JP4631579B2 - Laminated body - Google Patents

Description

  The present invention relates to a laminate.

  A laminate in which a thin film is laminated on a resin film is used as, for example, a display substrate on the front side and the back side of a display such as a liquid crystal display or an organic EL display. Conventionally, a substrate made of a glass plate has been put to practical use as a display substrate, but a substrate made of a resin plate that is lighter and less likely to break is desired. However, the resin does not have sufficient oxygen barrier properties, and there is a problem that the display deteriorates due to oxygen that has penetrated the substrate made of a resin plate and entered the display. Thus, it has been proposed to use a laminate formed by laminating a metal oxide layer as a layer having an oxygen barrier property on a resin film as a display substrate (for example, see Patent Document 1).

Japanese Patent Laid-Open No. 10-119171

However, the oxygen barrier property of this laminate is not sufficient, the oxygen permeability is about 0.2 cc / atm · m ² · day, and a laminate having a lower oxygen permeability has been demanded.
An object of the present invention is to provide a laminate in which a thin film is laminated on a resin film and has a low oxygen permeability.

  Therefore, as a result of intensive studies on the laminated body in order to examine the above problems, the laminated body has a resin film and three or more layers on at least one surface thereof, and the three layers are specified. In the case of three layers, the oxygen transmission rate of the laminate was found to be low, and the present invention was completed.

That is, the present invention provides the following laminate, display substrate, and display.
<1> It has three or more layers on at least one surface of a resin film, and each of the three layers is an inorganic layer and a number average particle diameter is 5 μm or less in order from the side closer to the resin film. Is a layer made of a resin containing an inorganic layered compound of 50 or more and 5000 or less, a layer made of a resin ,
The layer made of the resin is formed in contact with the layer made of the resin containing the inorganic layered compound,
A laminate comprising a resin constituting a resin layer containing an inorganic layered compound and a resin constituting the resin layer being the same resin .
<2> The resin constituting the resin layer of the resin containing the inorganic stratiform compound is an ethylene-norbornene copolymer, an ethylene-dmon copolymer, polyethylene terephthalate, polyethylene naphthalate, cellulose triacetate, cellulose diacetate , Selected from the group consisting of polyvinylidene chloride, polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polycarbonate resin, polysulfone resin, polyethersulfone resin, polyetheretherketone resin, and liquid crystal resin The laminate as described above, which is at least one kind of resin.
<3> The resin constituting the resin layer is an ethylene-norbornene copolymer, an ethylene-dmon copolymer, polyethylene terephthalate, polyethylene naphthalate, cellulose triacetate, cellulose diacetate, polyvinylidene chloride, polyvinylidene fluoride, The at least one resin selected from the group consisting of polytetrafluoroethylene, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polycarbonate resin, polysulfone resin, polyether sulfone resin, polyether ether ketone resin and liquid crystal resin. The laminated body in any one.
< 4 > The laminate according to any one of the above, wherein the inorganic layer is an inorganic layer made of metal, metal oxide, metal nitride, metal carbide, or metal oxynitride.
< 5 > The laminate according to any one of the above, wherein the inorganic layered compound is at least one inorganic layered compound selected from the group consisting of smectite, kaolinite, tetrasilic mica, sodium teniolite and talc.
< 6 > The laminate according to any one of the above, wherein the inorganic layered compound is contained while being substantially oriented in the plane direction.
< 7 > The laminate according to any one of the above, wherein the visible light transmittance is 80% or more.
< 8 > The laminate according to any one of the above, wherein the resin film has a thickness of 20 μm or more and 1000 μm or less, and the layer made of a resin containing an inorganic layered compound has a thickness of 1 nm or more and 10 μm or less.
< 9 > A display substrate comprising the laminate according to any one of the above.
< 10 > A display comprising the display substrate.

  Since the laminate of the present invention has a low oxygen permeability and is light, and its surface is excellent in flatness, it is useful for display substrates used in liquid crystal displays, organic EL displays and the like. Since the display substrate having a body is less deteriorated and durable, and provides a lightweight display, the present invention is extremely useful industrially.

  The laminate of the present invention comprises a resin plate having three or more layers on at least one surface of a resin film, and the three layers are arranged in order from the side closer to the resin film, an inorganic layer, a number average particle A layer made of a resin containing an inorganic layered compound having a diameter of 5 μm or less and an aspect ratio of 50 or more and 5000 or less, a layer made of a resin, and the reason is not clear, but a laminate having such a structure The body has a low oxygen permeability.

  Here, there is no limitation in particular as a resin film used for the laminated body of this invention, A transparent thing is preferable. Specific examples of the resin constituting the resin film include polyethylene (low density, high density), ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, and ethylene-octene copolymer. Polyolefin resins such as ethylene-norbornene copolymer, ethylene-domon copolymer, polypropylene, ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ionomer resin; polyethylene terephthalate, polybutylene terephthalate, polyethylene Polyester resins such as phthalates; nylon-6, nylon-6,6, metaxylenediamine-adipic acid condensation polymers; amide resins such as polymethylmethacrylamide; acrylic resins such as polymethylmethacrylate; polystyrene, Styrene-acrylonitrile resins such as tylene-acrylonitrile copolymer, styrene-acrylonitrile-butadiene copolymer, polyacrylonitrile; hydrophobic cellulose resins such as cellulose triacetate and cellulose diacetate; polyvinyl chloride, polyvinylidene chloride, polyfluoride Halogen-containing resins such as vinylidene chloride and polytetrafluoroethylene; hydrogen-bonding resins such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer, and cellulose derivatives; polycarbonate resins, polysulfone resins, polyethersulfone resins, polyetheretherketone resins And films of engineering plastic resins such as polyphenylene oxide resin, polymethylene oxide resin, and liquid crystal resin.

  And Tg of resin of the resin film used for the laminated body of this invention has preferable 150 degreeC or more, More preferably, it is 180 degreeC or more, More preferably, it is 200 degreeC or more.

  The thickness of the resin film is usually in the range of 20 μm to 1000 μm (1 mm), more preferably in the range of 20 μm to 500 μm, and still more preferably in the range of 20 μm to 300 μm.

  The laminate of the present invention has an inorganic layer on at least one surface of the resin film.

  The inorganic layer used in the present invention is an inorganic layer made of metal, metal oxide, metal nitride, metal carbide or metal oxynitride, and is preferably a thin film layer that is stable in the air. Include thin film layers of silica, alumina, titania, indium oxide, tin oxide, titanium oxide, zinc oxide, indium tin oxide, aluminum nitride, silicon nitride, silicon carbide, silicon oxynitride, and combinations thereof. More preferred are aluminum nitride, silicon nitride, silicon oxynitride, and still more preferred is a silicon oxynitride thin film layer in the sense of lowering the oxygen permeability.

  The thickness of the inorganic layer used in the present invention is preferably from 1 nm to 1000 nm (1 μm), more preferably from 10 nm to 500 nm. When the thickness is less than 1 nm, the oxygen transmittance tends to be high, and when it is thicker than 1000 nm, the light transmittance tends to decrease when the laminate of the present invention is used as a transparent display substrate.

  The laminate of the present invention is a resin containing an inorganic layered compound having a number average particle size of 5 μm or less and an aspect ratio of 50 to 5000 on at least one surface of the resin film on the inorganic layer. (Hereinafter, sometimes referred to as “inorganic-containing layer”).

  The inorganic layered compound used in the inorganic-containing layer in the present invention has an aspect ratio measured by the method described later of 50 to 5000 and a number average particle size of 5 μm or less. When the aspect ratio is less than 50, the oxygen permeability tends to increase. On the other hand, it is technically difficult to obtain an inorganic layered compound having an aspect ratio exceeding 5000. From the viewpoint of ease of production, the aspect ratio is more preferably 50 or more and 2000 or less, and further preferably in the range of 100 to 1000.

  Here, the aspect ratio (Z) of the inorganic layered compound used in the present invention is represented by the relationship Z = L / a. L is a number average particle diameter obtained by a dynamic light scattering method in a solvent. For example, see pages 169 to 179 of “Particle Size Measurement Technology” (1994, edited by the Powder Engineering Society). As a specific measuring device, a dynamic light scattering particle size distribution measuring device (for example, LB-550, manufactured by Horiba, Ltd.) can be exemplified. a is the unit thickness of the inorganic layered compound. The unit thickness a is a value that can be calculated by measuring the diffraction peak of the inorganic layered compound by powder X-ray diffraction.

  Furthermore, from the viewpoint of lowering the oxygen permeability of the resulting laminate, the number average particle size of the inorganic layered compound is preferably in the range of 50 nm to 2 μm, more preferably in the range of 200 nm to 1 μm, and in the range of 400 nm to 800 nm. A range is even more preferred.

  The inorganic layered compound refers to an inorganic compound having a layered structure in which unit crystal layers are stacked on each other, and a clay mineral having swelling / cleavage in a solvent can be preferably used. Specifically, smectite such as montmorillonite, hectorite, stevensite, saponite, beidellite, or kaolinite, dickite, nacrite, halloysite, antigolite, chrysotile, pyrophyllite, tetrasilic mica, sodium teniolite , Muscovite, margarite, talc, vermiculite, phlogopite, xanthophyllite, chlorite. Preferably, it is at least one inorganic layered compound selected from the group consisting of smectite, kaolinite, tetrasilic mica, sodium teniolite and talc from the viewpoint of dispersion described later.

  Examples of the resin constituting the inorganic-containing layer of the present invention include the same resins as those constituting the resin film. Preferably, from the viewpoint of heat resistance, an ethylene-norbornene copolymer and an ethylene-dmon copolymer are used. Polymer, polyethylene terephthalate, polyethylene naphthalate, cellulose triacetate, cellulose diacetate, polyvinylidene chloride, polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polycarbonate resin, polysulfone resin, polyether It is at least one resin selected from the group consisting of a sulfone resin, a polyether ether ketone resin and a liquid crystal resin, and more preferably an ethylene-norbornene copolymer, an ethylene-dmon copolymer, a polyvinyl alcohol. Ethylene - vinyl alcohol copolymer, polycarbonate resin, polysulfone resin, polyethersulfone resin. Even more preferably, an ethylene-norbornene copolymer or an ethylene-dmon copolymer is used to further reduce the water vapor transmission rate.

  In this inorganic-containing layer, the composition ratio (volume ratio) between the inorganic stratiform compound and the resin is usually in the range of the inorganic stratiform compound / resin volume ratio of 5/95 to 90/10, and the volume ratio of 5/95. A range of 95 to 50/50 is preferable. In addition, the flexibility of the film is improved in the range of 5/95 to 30/70, and the increase in oxygen permeability due to bending is reduced in the range of 7/93 to 17/83, or the peel strength is increased. The benefits of may appear. When the volume fraction of the inorganic layered compound is smaller than 5/95, the oxygen permeability tends to increase, and when it is larger than 90/10, the film forming property may not be good.

  Since the visible light transmittance of the laminate of the present invention is 80% or more, the thickness of the inorganic-containing layer is preferably 10 μm or less, and more preferably 1 μm or less. Since the oxygen permeability tends to be high, this thickness is preferably 10 nm or more. The visible light here means light having a wavelength in the range of 400 to 800 nm.

  The laminated body of this invention has an inorganic layer, an inorganic content layer, and the layer which further consists of resin in order from the side close | similar to a resin film in the at least one surface of a resin film.

  As the resin constituting the layer made of this resin, a transparent one is preferable. Specifically, a layer made of the same resin as the resin constituting the resin film can be mentioned as a more preferable one, and more preferably From the viewpoint of heat resistance, ethylene-norbornene copolymer, ethylene-dmon copolymer, polyethylene terephthalate, polyethylene naphthalate, cellulose triacetate, cellulose diacetate, polyvinylidene chloride, polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol , An ethylene-vinyl alcohol copolymer, a polycarbonate resin, a polysulfone resin, a polyether sulfone resin, a polyether ether ketone resin, and a liquid crystal resin, and even more preferably Len - norbornene copolymer, ethylene - Domon copolymer, polyvinyl alcohol, ethylene - vinyl alcohol copolymer, polycarbonate resin, polysulfone resin, polyethersulfone resin. Particularly preferred are an ethylene-norbornene copolymer and an ethylene-dmon copolymer in order to further lower the water vapor transmission rate.

  In the laminate of the present invention, the resin constituting the inorganic-containing layer and the resin constituting the layer made of the resin are preferably the same resin.

  The thickness of the layer made of this resin is usually in the range of 1 nm to 500 μm, and more preferably in the range of 100 nm to 10 μm.

  When the visible light transmittance is 80% or more, the laminate of the present invention configured as described above is not only used as a display-side substrate, but also as a display-side substrate (front-side). Display side), since it can be used as a substrate.

  In addition, since the surface of the laminate of the present invention is excellent in flatness, when the laminate is used as a display substrate, a transparent conductive film, antireflection film, and abrasion resistance are formed on the surface of the laminate. A film such as a film can be easily laminated and used. Here, the surface is the surface of the layer side made of resin in the laminate of the present invention.

  In addition, each layer and resin film which comprise the laminated body of this invention may contain a ultraviolet absorber, a coloring agent, antioxidant, etc. in the range which does not impair the effect of this invention.

Next, the manufacturing method of the laminated body of this invention is demonstrated.
The laminate of the present invention can be produced by sequentially forming an inorganic layer, an inorganic-containing layer, and a layer made of resin in this order on a resin film.

  First, the method for forming the inorganic layer made of the above-mentioned substance is not particularly limited, and examples thereof include a vacuum deposition method, a CVD method, a sputtering method, and a sol-gel method that are generally used industrially.

  Next, as a method of forming the inorganic-containing layer, it can be formed by a method that is usually used industrially. For example, a mixture of an inorganic layered compound, a resin, and a solvent is applied to a resin film on which an inorganic layer has been formed. Then, it can be formed by a coating method of drying and heat treatment, or a method of laminating a layer containing an inorganic layered compound. Coating methods include direct gravure method; reverse gravure method; micro gravure method; roll coating method such as two roll beat coating method and bottom feed three reverse coating method; doctor knife method; die coating method; dip coating method; And a coating method combining these methods. In the case of laminating, treatments such as a corona treatment and an anchor coating agent may be performed on the surfaces of both the resin film on which the inorganic layer is formed and the inorganic-containing layer to be joined.

  Here, in the inorganic layered compound, many of the respective particles are oriented so that the maximum surface thereof is substantially parallel to the surface of the laminate (this is referred to as “orientation in the plane direction”). preferable. When the inorganic layered compound is oriented, the oxygen permeability of the laminate tends to be further lowered. Therefore, as a coating method, a roll coating method and a doctor knife method, which are methods for applying a force (share) acting in a direction parallel to the surface of the flexible display substrate so as to orient the particles of the inorganic layered compound in the plane direction, are preferable. .

  The mixture of the inorganic layered compound, the resin and the solvent is obtained by using the above-mentioned inorganic layered compound and resin, for example, by swelling and cleaving the inorganic layered compound with the solvent and the solution obtained by dissolving the resin in the solvent. A method of mixing with a dispersion, a method of adding and dissolving a dispersion obtained by swelling and cleaving an inorganic layered compound with a solvent, and a method of swelling and cleaving by adding an inorganic layered compound to a solution obtained by dissolving a resin in a solvent And the kneaded product obtained by heating and kneading the resin and the inorganic stratiform compound is dissolved and dispersed in a solvent, and the former three are preferred.

  The solvent is preferably one that can swell the inorganic layered compound, and examples thereof include water, alcohols such as methanol, dimethylformamide, dimethyl sulfoxide, dichloromethane, chloroform, toluene, acetone, N-methylpyrrolidone, and the like.

  In producing a dispersion in which the inorganic layered compound is swollen and cleaved, it is preferable to perform a surface treatment of the inorganic layered compound in order to improve the dispersibility of the inorganic layered compound. As the surface treatment agent, a quaternary ammonium salt or the like is used.

Next, a resin layer is further formed on the resin film on which the inorganic layer and the inorganic-containing layer are formed.
As a method of forming a layer made of a resin, a coating liquid containing a resin is formed on the inorganic content layer of the resin film in which the inorganic layer and the inorganic content layer are formed in the same manner as the method of forming the inorganic content layer. Can be formed by a coating method in which is applied, dried, and heat treated, or a method of laminating a resin layer later. Specific examples of the coating method include the same method as that for forming the inorganic-containing layer. When laminating a resin layer on the inorganic-containing layer, the interface between the two may be treated with a corona treatment or an anchor coating agent.

As an example of a display using such a laminate of the present invention as a display substrate, a method for producing a flexible organic EL display will be described.
The flexible organic EL element has a light emitting layer between electrodes composed of a pair of an anode and a cathode, at least one of which is transparent. Organic EL element (anode / light emitting layer / electron transport layer / cathode) provided with an electron transport layer between the cathode and the light emitting layer (where “/” indicates that each layer is laminated adjacently) .), An organic EL device in which a hole transport layer is provided between the anode and the light emitting layer (anode / hole transport layer / light emitting layer / cathode), and an electron transport layer is provided between the cathode and the light emitting layer. And an organic EL device in which a hole transport layer is provided between the anode and the light emitting layer (anode / hole transport layer / light emitting layer / electron transport layer / cathode). For example, an anode is formed on a transparent or opaque display substrate, and a cathode is formed on a transparent or opaque display substrate (one of which is transparent). A hole transport layer and light emission are formed on the display substrate on which the anode is formed. A display substrate is formed by sequentially depositing a display substrate on which a cathode and a cathode are finally formed, with the electrodes facing each side so as to sandwich each layer, and sealing the edges. be able to.

  As the organic EL material used for the light emitting layer, a high molecular compound can be used even if it is a low molecular compound, and a high molecular compound is preferably used from the viewpoint of easy coating. In the low molecular weight compound, for example, as described in JP-A-57-51781 and 59-194393, for example, naphthalene derivatives, anthracene or derivatives thereof, perylene or derivatives thereof, polymethine series, xanthene series, Coumarin-based or cyanine-based dyes, 8-hydroxyquinoline or its derivative metal complex, aromatic amine, tetraphenylcyclopentadiene or its derivative, tetraphenylbutadiene or its derivative, etc. are used, and the light emitting layer is a powder. The film is formed by vacuum evaporation from, or by applying a solution and drying.

  In addition to the above poly (p-phenylene vinylene), polyfluorene (Japanese Journal of Applied Physics, Volume 30, L1941) can be used as an organic EL material. (1991)), polyparaphenylene derivatives (Advanced Materials (Adv. Mater.) Vol. 4, page 36 (1992)), and the like are used.

  As the hole transport material used for the hole transport layer, polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine compound group in a side chain or a main chain, polyaniline or a derivative thereof, polythiophene or a derivative thereof , Poly (p-phenylene vinylene) or a derivative thereof, or poly (2,5-thienylene vinylene) or a derivative thereof is used, and a film of the hole transport layer is coated with a mixed solution with a polymer binder, Dry to form.

  Electron transport materials used for the electron transport layer include oxadiazole derivatives, anthraquinodimethane or derivatives thereof, benzoquinone or derivatives thereof, naphthoquinone or derivatives thereof, anthraquinones or derivatives thereof, tetracyanoanthraquinodimethane or derivatives thereof, fluorenone Derivatives, diphenyldicyanoethylene or derivatives thereof, diphenoquinone derivatives, or metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, polyquinoxaline or derivatives thereof, polyfluorene or derivatives thereof, Or by applying a solution and drying.

  Furthermore, an anode and a cathode are required. As a material for the anode, a conductive metal oxide film, a translucent metal thin film, or the like is used. Specifically, indium oxide, zinc oxide, tin oxide, indium / tin / oxide (ITO), indium / zinc / oxide, gold, platinum, silver, copper, etc. are used, and vacuum deposition, sputtering, ion plate, etc. An anode is produced by a plating method or a plating method. Alternatively, an organic transparent conductive film such as polyaniline or a derivative thereof, polythiophene or a derivative thereof may be used as the anode.

  As a material for the cathode, a material having a small work function is preferable. For example, metals such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and their Two or more of these alloys, or an alloy of one or more of them and one or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin, graphite or graphite intercalation compound, etc. The cathode film can be produced by a vacuum deposition method, a sputtering method, or a laminating method in which a metal thin film is thermocompression bonded.

  By arranging these anodes and cathodes, light can be emitted in various patterns. In order to obtain planar light emission, the planar anode and cathode may be arranged so as to overlap each other. Further, in order to obtain a specific pattern of light emission, a method of installing a mask provided with a window of the specific pattern on the surface of the planar light emitting element, either the anode or the cathode, or both There is a method of forming electrodes in a specific pattern. A segment type display element capable of displaying numbers, letters, simple symbols, etc. can be obtained by forming a pattern by any of these methods and arranging several electrodes so that they can be turned ON / OFF independently. Further, in order to obtain a dot matrix element, both the anode and the cathode may be formed in stripes and arranged so as to be orthogonal to each other. Partial color display and multicolor display can be achieved by using a method of separately coating a plurality of phosphors having different emission colors, or by using a color filter or a fluorescence conversion filter. The dot matrix element may be passively driven or may be actively driven in combination with a TFT or the like.

  These display elements can be used as display devices for computers, televisions, mobile terminals, mobile phones, car navigation systems, video camera viewfinders, and the like. Furthermore, the planar light-emitting element is a self-luminous thin type, and can be suitably used as a planar light source for a backlight of a liquid crystal display device or a planar illumination light source. If a flexible substrate is used, it can be used as a curved light source or display device.

EXAMPLES Next, although an Example demonstrates this invention still in detail, this invention is not limited to an Example.
The oxygen permeability was measured with an oxygen permeability measuring device (manufactured by MOCON, OX-TRAN 2/20 type).
The water vapor transmission rate was measured with a water vapor transmission rate measuring device (Lyssy L80-5000).
Further, the flatness of the surface of the laminate was evaluated by the value of the surface average roughness (Ra). Here, the surface average roughness is a value corresponding to the arithmetic average roughness described in paragraph [4.2.1] of JIS B 0601 (revised on January 20, 2001) issued by the Japanese Standards Association, This is a value obtained from the average line of the cross-sectional curve on the surface of the resin layer, and was measured using an atomic force microscope (device name: Nanopics) manufactured by Seiko Instruments Inc.
Visible light transmittance was measured using a film thickness measurement system (apparatus name: MCPD-100) manufactured by Otsuka Electronics Co., Ltd.

Comparative Example 1
<First barrier layer deposition>
On a polyethersulfone (PES) substrate having a thickness of 200 μm, SiO _x N _y was deposited to a thickness of 30 nm at 120 ° C. by sputtering (oxynitride of silicon) (oxygen flow rate: nitrogen flow rate is 3: 2) This was used as the first barrier layer (oxygen barrier layer).

<Preparation of coating liquid (1)>
100 g of polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA117H (trade name)) is added to 1000 g of ion-exchanged water, heated to 95 ° C. with low speed stirring (1500 rpm, peripheral speed about 4 m / sec), and stirred for 1 hour The coating liquid (1) was obtained by making it melt | dissolve.

<Second barrier layer deposition>
On the first barrier layer, the coating liquid (1) was applied using a bar coater (manufactured by Tester Sangyo Co., Ltd., SA-203 type) so that the thickness after drying was 150 nm. A film was formed. Drying was performed by holding at 190 ° C. for 1 minute using a hot plate.

<Evaluation of laminate>
The oxygen permeability of the obtained substrate was measured at 23.5 ° C. and 60% RH (relative humidity). As a result, the substrate showed a high value of 2.9 cc / atm · m ² · day, and the SiO _x N _y layer Peeling easily occurred between the polyvinyl alcohols.

Example 1
<First barrier layer deposition>
On a polyethersulfone (PES) substrate having a thickness of 200 μm, SiO _x N _y was deposited by sputtering so as to have a thickness of 30 nm at 120 ° C. (oxygen flow rate: nitrogen flow rate is 3: 2). A barrier layer was formed.

<Preparation of coating liquid (2)>
100 g of polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA117H (trade name)) is added to 1000 g of ion-exchanged water, heated to 95 ° C. with low speed stirring (1500 rpm, peripheral speed of about 4 m / sec), and stirred for 1 hour. The solution (2) was obtained by dissolving. Subsequently, the temperature of the solution (2) was lowered to 65 ° C. with stirring, and then an aqueous alcohol solution obtained by previously mixing 400 g of ion-exchanged water and 94 g of 1-butanol was slowly added dropwise to the solution (2). . After completion of dropping, 50 g of high purity natural montmorillonite (Kunimine Kogyo Co., Ltd., Kunipia G (trade name), number average particle size 500 nm, aspect ratio is 200 or more) is added as a powder at 65 ° C. as an inorganic layered compound. Then, the stirring condition was switched to high speed stirring (3000 rpm, peripheral speed about 8 m / sec), and the mixture was stirred and dispersed for 90 minutes to obtain a resin composition mixed solution (2). Next, the resin composition mixed solution (2) is passed through an ultra-high pressure homogenizer (manufactured by Microfluidics Corporation, M110-E / H type) and treated once at 1.750 kgf / cm ² , so that the dispersibility is good and uniform. A coating liquid (2) was obtained. The solid content concentration of the coating liquid (2) was about 7.6% by weight.

<Second barrier layer deposition>
On the first barrier layer, a coating liquid (2) is formed to a thickness of 150 nm using polyvinyl alcohol containing an inorganic layered compound using a bar coater (manufactured by Tester Sangyo, SA-203 type). Filmed. Drying was performed by holding at 190 ° C. for 1 minute on a hot plate.

<Preparation of coating liquid (1)>
100 g of polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA117H (trade name)) is added to 1000 g of ion-exchanged water, heated to 95 ° C. with low speed stirring (1500 rpm, peripheral speed about 4 m / sec), and stirred for 1 hour The coating liquid (1) was obtained by making it melt | dissolve.

<Third barrier layer deposition>
On the second barrier layer, the coating liquid (1) was applied to a thickness of 150 nm using a bar coater (manufactured by Tester Sangyo, SA-203 type) to form a polyvinyl alcohol layer. Drying was performed by holding at 190 ° C. for 1 minute using a hot plate.

<Evaluation of laminate>
As a result of measuring the oxygen transmission rate of the laminate made of the resin plate under 23.5 ° C. and 60% RH, it showed a low value of 1 × 10 ⁻³ cc / atm · m ² · day or less. The water vapor transmission rate was as low as 2.0 g / atm · m ² · day at 40 ° C. The transmittance of visible light was 80% or higher at any wavelength in the range of 400 to 800 nm. For example, the transmittance of light having a wavelength of 550 nm was 90.6%. Moreover, peeling between the SiO _x N _y layer and the polyvinyl alcohol did not occur. The cross section of the laminate made of the obtained resin plate was observed by SEM, and it was confirmed that the layered compound in the second barrier layer was oriented. Moreover, the value of the surface average roughness (Ra) of the laminated body was 0.2 nm, and it was found that the surface was excellent in flatness.

Example 2
<First barrier layer deposition>
On a polyethersulfone (PES) substrate having a thickness of 200 μm, SiO _x N _y was deposited by sputtering so as to have a thickness of 30 nm at 120 ° C. (oxygen flow rate: nitrogen flow rate is 3: 2). A barrier layer was formed.

<Preparation of coating liquid (3)>
In 80 g of toluene, 20 g of an ethylene-norbornene copolymer (manufactured by JSR, ARTON F5023 (trade name)) was added and dissolved by stirring at room temperature for 4 hours under low speed stirring to obtain a resin solution (3). In addition, 2.5g of organically modified natural montmorillonite (manufactured by Hojun Co., Ltd., Sven (trade name), number average particle size 560nm, aspect ratio of 200 or more) in powder form is added to 47.5g of toluene while stirring at low speed. While cooling with ice water, the mixture was dispersed with a homogenizer (10000 rpm, 10 min) to obtain a dispersion (3). The resin solution (3) and the dispersion liquid (3) were mixed at a weight ratio of 10:17, stirred for 3 minutes and defoamed for 2 minutes to obtain a uniform coating liquid (3) with good dispersibility. The solid content concentration of the coating liquid (3) was about 10.6% by weight.

<Second barrier layer deposition>
On the first barrier layer, a layer made of an ethylene-norbornene copolymer containing an inorganic layered compound with a coating liquid (3) using a bar coater (manufactured by Tester Sangyo, SA-203 type) to a thickness of 150 nm The film was formed as follows. Drying was performed by holding at 60 ° C. for 10 minutes with a hot plate.

<Preparation of coating liquid (4)>
20 g of ethylene-norbornene copolymer (manufactured by JSR, ARTONF5023 (trade name)) was added to 80 g of toluene, and the mixture was dissolved by stirring at room temperature for 4 hours under low speed stirring to obtain a coating liquid (4).

<Third barrier layer deposition>
On the second barrier layer, the coating liquid (4) was applied to a thickness of 150 nm using a bar coater (manufactured by Tester Sangyo, SA-203 type), and an ethylene-norbornene copolymer layer was formed. A film was formed. Drying was performed using a hot plate and holding at 60 ° C. for 10 minutes.

<Evaluation of laminate>
As a result of measuring the oxygen transmission rate of the laminate made of the resin plate under 23.5 ° C. and 60% RH, it showed a low value of 1 × 10 ⁻³ cc / atm · m ² · day or less. The water vapor transmission rate was as low as 0.6 g / atm · m ² · day at 40 ° C. The transmittance of visible light was 80% or more at any wavelength in the range of 400 to 800 nm. For example, the transmittance of light having a wavelength of 550 nm was 82.6%. Further, no peeling occurred between the SiO _x N _y layer and the ethylene-norbornene copolymer layer. The cross section of the laminate made of the obtained resin plate was observed by SEM, and it was confirmed that the layered compound in the second barrier layer was oriented. Moreover, the value of the surface average roughness (Ra) of a laminated body is 0.7 nm, and it turned out that the surface is excellent in flatness.

Claims (10)

It has three or more layers on at least one surface of the resin film, and each of the three layers is an inorganic layer made of silicon oxynitride in order from the side close to the resin film, and the number average particle diameter is 5 μm or less. A layer made of a resin containing an inorganic layered compound having an aspect ratio of 50 or more and 5000 or less, a layer made of a resin,
The layer made of the resin is formed in contact with the layer made of the resin containing the inorganic layered compound,
A laminate comprising a resin constituting a resin layer containing an inorganic layered compound and a resin constituting the resin layer being the same resin.   The laminate according to claim 1, wherein the inorganic layer is a layer formed by sputtering.   The resin constituting the resin layer of the resin layer containing the inorganic stratiform compound is an ethylene-norbornene copolymer, an ethylene-domon copolymer, polyethylene terephthalate, polyethylene naphthalate, cellulose triacetate, cellulose diacetate, polychlorinated At least one selected from the group consisting of vinylidene, polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polycarbonate resin, polysulfone resin, polyether sulfone resin, polyether ether ketone resin, and liquid crystal resin. The laminate according to claim 1 or 2, which is a seed resin.   Resins constituting the resin layer are ethylene-norbornene copolymer, ethylene-dmon copolymer, polyethylene terephthalate, polyethylene naphthalate, cellulose triacetate, cellulose diacetate, polyvinylidene chloride, polyvinylidene fluoride, polytetrafluoro. It is at least one resin selected from the group consisting of ethylene, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polycarbonate resin, polysulfone resin, polyether sulfone resin, polyether ether ketone resin, and liquid crystal resin. 4. The laminate according to any one of 3 above. The laminate according to any one of claims 1 to 4 , wherein the inorganic layered compound is at least one inorganic layered compound selected from the group consisting of smectite, kaolinite, tetrasilic mica, sodium teniolite and talc. The laminate according to any one of claims 1 to 5 , wherein the inorganic layered compound is contained while being substantially oriented in the plane direction. The laminate according to any one of claims 1 to 6 , wherein the visible light transmittance is 80% or more. The laminate according to any one of claims 1 to 7 , wherein the resin film has a thickness of 20 µm or more and 1000 µm or less, and a layer made of a resin containing an inorganic stratiform compound has a thickness of 1 nm or more and 10 µm or less. Display substrate characterized by having a laminate according to any one of claims 1-8. A display comprising the display substrate according to claim 9 .