JP2007136800A - Gas-barrier laminated film and image display element using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminated film excellent in flexibility, heat resistance, and gas-barrier properties. <P>SOLUTION: In the gas-barrier laminated film having at least one inorganic layer (A) and at least one amorphous carbon layer (B) containing amorphous carbon as a main component on a substrate film, the ratio of the number of oxygen atoms to the number of carbon atoms on the surface of the amorphous carbon layer (B) is at least 0.01. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a laminated film having excellent heat resistance, durability and gas barrier properties, and specifically relates to a laminated gas barrier laminated film suitable for various organic device substrates and coating films. Furthermore, the present invention relates to an image display element such as a liquid crystal display device and an organic EL element having excellent durability and flexibility using the gas barrier film.

  With the spread of personal computers and portable information terminals, the demand for light and thin electronic displays is increasing rapidly. Currently, glass substrates are mainly used as substrates for image display elements such as liquid crystal display elements that are most prevalent and organic EL elements that have recently attracted attention due to high visibility due to self-coloring properties. However, recently, it has been studied to use a thin, light, and flexible plastic film as a substrate instead of a heavy and easily broken glass substrate. From the viewpoint of weight reduction of the image display element, durability against impact, flexibility, and the like, it is preferable to use a flexible plastic substrate as the substrate of the liquid crystal display element or the organic EL element. In addition, since the transparent plastic substrate can be easily enlarged and a roll-to-roll production method can be applied, the productivity is higher than the glass substrate and it is advantageous in terms of cost reduction. However, since the plastic substrate is inferior in heat resistance and gas barrier property as compared with the glass substrate, it is not suitable for producing a high-definition pattern and has a drawback that it lacks durability.

  Many studies have been reported so far to improve such defects in plastic substrates. For example, in order to suppress permeation of water vapor or oxygen, it is known to provide a layer (gas barrier film) that suppresses permeation of various gases to the base material. Examples of such layers include inorganic materials such as silicon oxide films, silicon nitride films, silicon oxynitride films, silicon carbide films, aluminum oxide films, aluminum oxynitride films, titanium oxide films, zirconium oxide films, and diamond-like carbon films. Thin films and the like are known. Also known are gas barrier films in which these inorganic thin films having high gas barrier properties and flexible organic thin films are laminated (see, for example, Patent Documents 1 to 5).

As a gas barrier laminated film used for a packaging material or a liquid crystal display element, for example, a film obtained by depositing silicon oxide on a plastic film (see Patent Document 1) is known, and 0.5 g / m ² · day is known. It has a degree of water vapor barrier property. However, gas barrier properties and bending resistance are insufficient for use as a flexible organic EL display substrate, and further improvements have been desired.

Patent Document 2 discloses a gas barrier film using amorphous diamond-like carbon. However, the water vapor barrier property is only ² g / m ² · day, and the gas barrier property is insufficient for use as an organic EL display substrate.

  Furthermore, a gas barrier laminate film (see Patent Document 3) in which an organic / inorganic hybrid polymer layer and an inorganic layer are combined is also known. However, the level of gas barrier properties of this film is not sufficient, and further improvement has been desired.

  On the other hand, a gas barrier laminate film (see Patent Document 4) in which organic layers and inorganic layers are alternately laminated has also been proposed. However, although this film is flexible, the heat resistance of the organic layer and the gas barrier property for use as an organic EL display substrate are insufficient, and further improvements have been desired.

Further, Patent Document 5 describes an organic electroluminescence display panel in which a barrier film composed of an inorganic layer and a polymer layer is formed on a resin substrate. In the organic electroluminescence display panel, a plasma treatment is performed on an exposed portion of the polymer layer sandwiched between inorganic layers, which is not covered with the inorganic layer, and gas barrier properties are imparted to the exposed portion of the polymer layer.
JP-A-6-136159 JP-A-11-26155 JP 2002-301793 A JP 2003-53881 A JP 2005-123012 A

  The present invention has been made in view of the above problems, and a first object of the present invention is to provide a laminated film having excellent bending resistance, heat resistance, and gas barrier properties, and in particular, having a bending resistance of gas barrier performance. There is. A second object of the present invention is to provide an image display device, particularly an organic EL device, having high definition and high durability, using the gas barrier laminate film.

  The object of the present invention is achieved by the following means.

(1) The substrate film has at least one inorganic layer (A) and at least one amorphous carbon layer (B) mainly composed of amorphous carbon, and at least one amorphous carbon layer (B) The ratio of (number of oxygen atoms / number of carbon atoms) on the surface of 0.01) is 0.01 or more.

(2) The ratio of (number of oxygen atoms / number of carbon atoms) on the surface of at least one amorphous carbon layer (B) is 0.01 or more due to the surface treatment. The gas barrier laminate film according to (1).
(3) The gas barrier laminate film according to (2), wherein the surface treatment is an oxygen plasma treatment.
(4) The gas barrier laminate film according to any one of (1) to (3), wherein the inorganic layer (A) layer and the amorphous carbon layer (B) are alternately laminated.
(5) Oxygen permeability at 38 ° C. and 90% relative humidity is 0.01 ml / m ² · day · atm or less, and water vapor permeability at 38 ° C. and 90% relative humidity is 0.01 g / m ² · day The gas barrier laminate film according to any one of (1) to (4), which is as follows.
(6) The gas barrier laminate film according to any one of (1) to (5), wherein the gas barrier laminate film has gas barrier properties even after a bending test.
(7) An image display element using the gas barrier laminate film according to any one of (1) to (6).

  The gas barrier laminate film of the present invention preferably has a gas barrier layer comprising at least one inorganic compound and at least one layer containing amorphous carbon on a transparent plastic film substrate.

  Furthermore, in the gas barrier laminate film of the present invention, the inorganic compound constituting the gas barrier layer preferably has a metal oxide or a metal nitride as a main component.

  Furthermore, in the gas barrier laminate film of the present invention, the inorganic compound constituting the gas barrier layer may be formed of a metal oxide such as silicon, aluminum, titanium, zirconium, or tin, a nitride, or a composite thereof.

  Furthermore, in the gas barrier laminate film of the present invention, it is preferable that the inorganic layer and the amorphous carbon layer are alternately laminated on a transparent substrate film.

  Furthermore, the gas barrier laminate film of the present invention preferably has a reactive functional group formed on the amorphous carbon surface by subjecting the surface of the amorphous carbon layer to a surface treatment.

Furthermore, the gas barrier laminate film of the present invention has an oxygen permeability of less than 0.005 ml / m ² · day · atm at 38 ° C. and 90% relative humidity, and a water vapor permeability at 38 ° C. and 90% relative humidity. It is preferably less than 0.005 g / m ² · day.

Furthermore, the gas barrier laminate film of the present invention has an oxygen permeability of less than 0.005 ml / m ² · day · atm at 38 ° C. and 90% relative humidity, and 38 ° C. and 90% relative humidity even after the bending test. It is preferable that the water vapor transmission rate is less than 0.005 g / m ² · day.

  The second object of the present invention is achieved by an organic EL device using the gas barrier laminate film as a substrate.

  ADVANTAGE OF THE INVENTION According to this invention, the gas barrier property laminated film which has the outstanding bending resistance, heat resistance, and gas barrier property, and has especially bending resistance of gas barrier performance can be provided. Furthermore, according to the present invention, an image display element such as a liquid crystal display device and an organic EL element having high definition and high durability can be provided.

  Hereinafter, the gas barrier film of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

<Gas barrier laminate film>
The gas barrier laminate film of the present invention has at least one inorganic layer (A) and at least one amorphous carbon layer (B) containing amorphous carbon on the substrate film, and at least one amorphous carbon layer. The ratio of (number of oxygen atoms / number of carbon atoms) on the surface of the layer (B) is 0.01 or more. The ratio of (number of oxygen atoms / number of carbon atoms) is more preferably 0.05 or more, and further preferably 0.1 or more. The ratio of (number of oxygen atoms / number of carbon atoms) on the surface can be measured by X-ray photoelectron spectroscopy (XPS). The evaluation of (number of oxygen atoms / number of carbon atoms) by the X-ray photoelectron spectroscopy (XPS) is, for example, a known X-ray photoelectron spectroscopy (XPS) apparatus (for example, 1600S type X-ray photoelectron spectrometer manufactured by PHI). Specifically, it can be evaluated by measuring the elemental composition contained in the amorphous carbon layer according to the present invention.
XPS is one of the typical surface analyzers, and is used for analysis of elemental and chemical bonding states in a submicron order depth region by using etching from a solid surface. When the chemical bond state of each element is different, the bond energy slightly changes and is detected in a distinguishing manner. This makes it possible to analyze the functional groups of organic substances (such as the determination of C—O and C═O) and the oxidation state of inorganic substances. Analysis (quantification of metal and oxidation state) is possible. Therefore, since the C—O, C═O bond is formed on the surface of the amorphous carbon layer subjected to the oxygen plasma treatment in the present invention, the ratio of the number of oxygen atoms to the number of carbon atoms can be determined from these composition ratios.
By setting the ratio of (number of oxygen atoms / number of carbon atoms) to 0.01 or more on the surface of at least one amorphous carbon layer (B), the gas barrier film has excellent bending resistance, heat resistance and gas barrier properties. While being able to provide, the bending resistance of gas barrier performance can also be provided. For this reason, the gas barrier performance of the gas barrier laminate film of the present invention does not deteriorate even after being bent or heated.

[Amorphous carbon layer]
In the gas barrier laminate film of the present invention, the amorphous carbon layer (B) is a layer mainly composed of amorphous carbon. Here, the layer containing amorphous carbon as a main component means a layer containing 50% by mass or more of amorphous carbon with respect to the total solid content of the layer. As content of the said amorphous carbon, 75 mass% or more is preferable with respect to the total solid of an amorphous carbon layer, and 90 mass% or more is still more preferable.

(Amorphous carbon)
The amorphous carbon used in the present invention will be described. The “amorphous carbon” in the present invention is also called diamond-like carbon (DLC), sp3 An amorphous carbon film mainly composed of bonds, which contains diamond, graphite, and polymer components. As parameters governing these structures, the hydrogen atom content, the sp3 carbon component ratio, and the like can be considered, and the physical properties of the amorphous carbon film differ greatly depending on them. In general, the lower the hydrogen content, the harder the film is formed, and the higher the hydrogen content, the softer the carbon film is formed.

  The amorphous carbon film has a characteristic of low gas permeability such as water vapor and oxygen. As described in JP-A-6-344495, an amorphous carbon film is provided with an amorphous carbon thin film on one surface. It has been proposed to form a gas barrier film.

  Examples of the amorphous carbon film forming method include an ion plating method and a sputtering method, for example, a physical vapor deposition method such as ion beam sputtering, a plasma CVD method, a microwave CVD method, and a high frequency CVD method. In these methods, plasma is generated in a film forming apparatus to ionize or excite a gas (source gas). As a method for ionizing or exciting a gas, for example, a method for plasma decomposition by applying a DC voltage, a method for plasma decomposition by applying a high frequency, a method for plasma decomposition by microwave discharge, or a plasma decomposition by electron cyclotron resonance. And a method of thermally decomposing by heating with a hot filament.

  As a raw material gas for forming an amorphous carbon film, a gas containing carbon atoms and hydrogen atoms is used. Examples of such gases include alkane-based gases such as methane, ethane, propane, butane, pentane, and hexane; alkene-based gases such as ethylene, propylene, butene, and pentene; and alkadiene-based gases such as pentadiene and butadiene. Alkyne gases such as acetylene and methylacetylene; aromatic hydrocarbon gases such as benzene, toluene, xylene, indene, naphthalene and phenanthrene; cycloalkane gases such as cyclopropane and cyclohexane; methanol, ethanol, etc. Alcohol-based gases; ketone-based gases such as acetone and methyl ethyl ketone; and aldehyde-based gases such as methanal and ethanal. The said gas can be used individually or in combination of 2 or more types.

  Other source gases include: a mixed gas of the above gas and hydrogen gas; a mixed gas of the above gas and an oxygen-containing gas such as carbon monoxide gas or carbon dioxide gas; hydrogen gas and carbon monoxide gas; A mixed gas of oxygen-containing gas such as carbon dioxide gas; a mixed gas of oxygen gas, water vapor, and oxygen-containing gas such as carbon monoxide gas or carbon dioxide gas. Furthermore, as other source gas, the mixed gas of the said source gas and a noble gas is also mentioned. Examples of such source gas include helium, argon, neon, xenon, and the like, and these can be used alone or in combination of two or more.

  The gas barrier laminate film of the present invention is characterized in that the ratio of (number of oxygen atoms / number of carbon atoms) on the surface of at least one of the amorphous carbon layers formed on the substrate film is 0.01 or more. A method for realizing such a ratio of (number of oxygen atoms / number of carbon atoms) is not particularly limited, but is preferably realized by performing a surface treatment. Above all, functional groups such as hydroxyl groups and carboxyl groups can be introduced on the surface of the amorphous carbon layer, increasing the affinity with the inorganic layer and improving the adhesion between the amorphous carbon layer (B) and the inorganic layer (A). Such surface treatment is preferable. By performing such surface treatment, the gas barrier performance can be maintained even after the film is bent.

  Examples of the surface treatment method for the amorphous carbon layer include ultraviolet light treatment in an atmosphere in which oxygen is present, or oxygen plasma treatment in an atmosphere in which at least oxygen is present. As the surface treatment method of the amorphous carbon layer, oxygen plasma treatment is preferable. The oxygen plasma treatment can be performed, for example, by introducing oxygen into the chamber using a normal plasma CVD apparatus or the like. The surface treatment here does not include forming the inorganic layer (A) on the amorphous carbon layer (B).

  The thickness of the amorphous carbon layer is preferably 10 nm to 5 μm, more preferably 10 nm to 0.5 μm, from the viewpoint of suppressing defects in the inorganic layer due to external forces such as bending.

(Inorganic layer)
In the present invention, the inorganic layer is preferably a layer made of a metal oxide such as silicon, aluminum, titanium, zirconium or tin, or an inorganic material such as nitride or oxynitride, and may be formed of a composite thereof. Good.

  Examples of the method for forming the inorganic layer include physical vapor deposition (PVD) such as vapor deposition, sputtering, or ion plating, various chemical vapor deposition (CVD), and liquids such as plating and sol-gel. There is a phase growth method. Among these, chemical vapor deposition (CVD) and physical vapor deposition are used because they avoid the influence of heat on the substrate film during the formation of the inorganic layer, have a high production rate, and are easy to obtain a uniform thin film layer. (PVD) is preferred. Moreover, it is also preferable to form an inorganic layer by a sol-gel method from the viewpoint that a thick film can be easily obtained. Here, the thick film refers to a film in the range of 100 nm to 1 μm.

  The thickness of the inorganic layer in the present invention is preferably 30 nm to 1 μm, and more preferably 50 to 200 nm. When the thickness of the inorganic layer is in the range of 50 nm to 1 μm, it is difficult to be affected by defective portions or portions having low density between crystals, and high gas barrier properties can be obtained. Further, even when it is deformed, the destruction of the inorganic layer can be reduced, which is preferable in practice.

[Substrate film]
The substrate film used in the gas barrier laminate film of the present invention is preferably made of a heat-resistant material so that it can be used as an image display element described later. Preferably, a plastic film having a glass transition temperature (Tg) of 100 ° C. or higher and / or a linear thermal expansion coefficient of 40 ppm / ° C. or lower and high heat resistance is used as the substrate film. The Tg and linear expansion coefficient of the substrate film can be changed by an additive or the like.

The polymer that can be used for the substrate film in the present invention may be either a thermoplastic polymer or a thermosetting polymer. The thermoplastic polymer preferably has a Tg of a single polymer of 130 to 300 ° C, more preferably 160 to 250 ° C. Further, in order to achieve optical uniformity, an amorphous polymer is preferable.
Examples of such a thermoplastic polymer include the following (the temperature in parentheses indicates the Tg of the polymer).

  Polycarbonate (PC: 140 ° C.), alicyclic polyolefin (for example, ZEONOR 1600: 160 ° C. manufactured by Nippon Zeon Co., Ltd.), polyarylate (PAr: 210 ° C.), polyethersulfone (PES: 220 ° C.), polysulfone (PSF: 190 ° C), cycloolefin copolymer (COC: compound of JP 2001-150584 A, 162 ° C.), fluorene ring-modified polycarbonate (BCF-PC: compound of JP 2000-227603 A: 225 ° C.), alicyclic modification Polycarbonate (IP-PC: compound of JP 2000-227603 A: 205 ° C.), acryloyl compound (compound of JP 2002-80616 A: 300 ° C. or higher). In particular, when transparency is required, it is preferable to use an alicyclic polyolefin or the like.

  Examples of the thermosetting polymer include epoxy resins and radiation curable resins. Examples of the epoxy resin include polyphenol type, bisphenol type, halogenated bisphenol type, and novolac type. A known curing agent can be used as the curing agent for curing the epoxy resin. Examples thereof include curing agents such as amines, polyaminoamides, acids and acid anhydrides, imidazoles, mercaptans, and phenol resins. Among them, from the viewpoints of solvent resistance, optical properties, thermal properties, etc., acid anhydrides and polymers containing acid anhydride structures or aliphatic amines are preferably used, and acid anhydrides and acid anhydride structures are particularly preferred. It is a polymer containing. Furthermore, it is preferable to add an appropriate amount of a known curing catalyst such as tertiary amines and imidazoles.

  The radiation curable resin is a resin that cures when irradiated with radiation such as ultraviolet rays and electron beams. Specifically, it is an unsaturated diamine, methacryloyl group, vinyl group, or other unsaturated bisphenol in a molecule or a single structure. A resin containing a double bond. Among these, an acrylic resin containing an acryloyl group is particularly preferable. The radiation curable resin may be one kind of resin or a mixture of several kinds of resins, but an acrylic resin having two or more acryloyl groups in a molecule or unit structure may be used. preferable. Examples of such polyfunctional acrylate resins include, but are not limited to, urethane acrylates, ester acrylates, epoxy acrylates, and the like.

  When an ultraviolet curing method is used for curing these radiation curable resins, it is preferable to add an appropriate amount of a known photoreaction initiator to the aforementioned radiation curable resin.

  In order to further enhance the interaction with the polymer molecule, an alkoxysilane hydrolyzate or a silane coupling agent may be mixed with the epoxy resin and the radiation curable resin. As the silane coupling agent, one having a hydrolyzable reactive group such as a methoxy group, an ethoxy group, and an acetoxy group and the other having an epoxy group, a vinyl group, an amino group, a halogen group, and a mercapto group In this case, those having a vinyl group having the same reactive group are particularly preferable for fixing to the main component resin. For example, “KBM-503” and “KBM-803” manufactured by Shin-Etsu Chemical Co., Ltd. are preferable. “A-187” manufactured by Nippon Unicar Co., Ltd. is used. These addition amounts are preferably 0.2 to 3% by mass.

  Moreover, it is also suitable to perform surface treatments such as plasma irradiation on the substrate film of the present invention which is a base material.

  Since the gas barrier laminate film of the present invention is used as an image display element such as a display, the transparent substrate film, that is, the light transmittance is 80% or more, preferably 85% or more, more preferably 90% or more. It is preferable to use a certain substrate film. If the light transmittance of the substrate film is 80% or more, it can be suitably used as a substrate film for an organic EL device described later.

  In addition, it is needless to say that an opaque material can be used for applications that do not necessarily require transparency, such as a case where the display is not installed on the observation side or an opaque packaging material. Examples thereof include polyimide, polyacrylonitrile, and known liquid crystal polymers.

  The light transmittance used as a scale of transparency in this specification is determined by measuring the total light transmittance and the amount of scattered light using the method described in JIS-K7105, that is, using an integrating sphere light transmittance measuring device. It can be calculated by subtracting the diffuse transmittance from the light transmittance.

Furthermore, the gas barrier laminate film of the present invention may be provided with various functional layers in addition to the inorganic layer (A) and the amorphous carbon layer (B). Examples of the functional layer include an optical functional layer such as an antireflection layer, a polarizing layer, a color filter, and a light extraction efficiency improving layer; a mechanical functional layer such as a hard coat layer and a stress relaxation layer; an antistatic layer and a conductive layer. An electric functional layer such as: an antifogging layer; an antifouling layer; a layer to be printed, and the like. These functional layers are installed on the substrate film, the inorganic layer (A), between the inorganic layer (A) and the amorphous carbon layer (B), or on the opposite side of the substrate film on which the inorganic layer (A) is installed. May be.
Furthermore, a gas barrier laminate layer in which at least an inorganic gas barrier layer, an organic layer, and an inorganic gas barrier layer are laminated in this order may be provided on the opposite side of the hygroscopic layer from the substrate film. The gas barrier laminate layer suppresses the dimensional change of the film substrate by preventing intrusion of water molecules from the opposite side of the film, thereby preventing stress concentration and destruction to the gas barrier layer, resulting in a highly durable display. It has the feature that it can.

  In addition, the thickness of the substrate film in the present invention is preferably 30 μm to 300 μm, more preferably 40 μm to 200 μm, from the viewpoint of mechanical strength and the like.

[Configuration of each layer]
The gas barrier laminate film of the present invention is constituted by laminating at least one inorganic layer (A) and at least one amorphous carbon layer (B).
The order of lamination of the inorganic layer (A) and the amorphous carbon layer (B) is not particularly limited, but the inorganic layer (A) and the amorphous carbon layer (B) are formed in this order from the substrate film side. It is preferable that the inorganic layers (A) and the amorphous carbon layers (B) are alternately laminated.
In the present invention, the number of constituents of the inorganic layer (A) and the amorphous carbon layer (B) is not particularly limited and can be selected according to the purpose. Examples of the layer structure of the gas barrier laminate film of the present invention include substrate film: inorganic layer (A): amorphous carbon layer (B): inorganic layer (A).

Moreover, the aspect which laminates | stacks an inorganic layer (A) and an amorphous carbon layer (B) on both surfaces of a substrate film is also suitable.
The gas barrier laminate film of the present invention has an oxygen transmission rate of 0.01 ml / m ² · day · atm or less at 38 ° C. and a relative humidity of 90%, and a water vapor transmission rate of 0.01 g at 38 ° C. and a relative humidity of 90%. / M ² · day or less is preferable. When the oxygen permeability and water vapor permeability are in the above ranges, sufficient gas barrier ability can be exhibited. The oxygen permeability is preferably 0.005 ml / m ² · day · atm or less. The water vapor transmission rate is preferably 0.005 g / m ² · day or less.
The gas barrier laminate film of the present invention preferably has gas barrier properties even after a bending test. Here, “having gas barrier properties even after the bending test” means that the oxygen permeability at 38 ° C. and 90% relative humidity is 0.01 ml / m ² · day · atm or less as a result of the test of Test Example 2 described later. And the water vapor transmission rate at 38 ° C. and 90% relative humidity is 0.01 g / m ² · day or less.

<Image display element>
The image display element in the present invention refers to, for example, a circularly polarizing plate, a liquid crystal display element, electronic paper, an organic EL element, and the like. Although the use of the gas barrier laminate film of the present invention is not particularly limited, it can be suitably used as a substrate or a sealing film of an image display element.

(Circularly polarizing plate)
The circularly polarizing plate can be produced by laminating a λ / 4 plate and a polarizing plate on the gas barrier laminate film of the present invention. In this case, the lamination is performed so that the slow axis of λ / 4 and the absorption axis of the polarizing plate are 45 °. As such a polarizing plate, it is preferable to use what is extended | stretched in the 45 degree direction with respect to the longitudinal direction (MD), For example, what is described in Unexamined-Japanese-Patent No. 2002-865554 can be used suitably.

(Liquid crystal display element)
The liquid crystal display device can be roughly classified into a reflective liquid crystal display device and a transmissive liquid crystal display device. The reflective liquid crystal display device includes a lower substrate, a reflective electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, a transparent electrode, an upper substrate, a λ / 4 plate, and a polarizing film in order from the bottom. The gas barrier laminate film of the present invention can be used as the transparent electrode and the upper substrate. When the reflective liquid crystal display device has a color display function, a color filter layer may be further provided between the reflective electrode and the lower alignment film, or between the upper alignment film and the transparent electrode. preferable.

  Further, the transmissive liquid crystal display device includes, in order from the bottom, a backlight, a polarizing plate, a λ / 4 plate, a lower transparent electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, an upper transparent electrode, an upper substrate, and λ / 4. It has the structure which consists of a board and a polarizing film. Among these, the gas barrier laminate film of the present invention can be used as the upper transparent electrode and the upper substrate. Further, when the transmissive liquid crystal display device has a color display function, a color filter layer is further provided between the lower transparent electrode and the lower alignment film, or between the upper alignment film and the transparent electrode. It is preferable to provide it.

  The structure of the liquid crystal layer is not particularly limited. OCB (Optically Compensated Bend) type or CPA (Continuous Pinwheel Alignment) type is preferable.

(Organic EL device)
An organic EL element has a cathode and an anode on a substrate, and an organic compound layer including an organic light emitting layer (hereinafter sometimes simply referred to as “light emitting layer”) between both electrodes. In view of the properties of the light emitting element, at least one of the anode and the cathode is preferably transparent.

  When the gas barrier laminate film of the present invention is used for organic EL or the like, JP-A-11-335661, JP-A-11-335368, JP-A-2001-192651, JP-A-2001-192652, JP 2001-192653, JP 2001-335776, JP 2001-247859, JP 2001-181616, JP 2001-181617, JP 2002-181816, JP 2002. -181617, Japanese Patent Application Laid-Open No. 2002-056776, etc., and Japanese Patent Application Laid-Open Nos. 2001-148291, 2001-221916, 2001-231443, etc. are used in combination. preferable. That is, the gas barrier laminate film of the present invention can be used as a substrate film and / or a protective film when forming an organic EL element.

  The features of the present invention will be described more specifically with reference to examples and comparative examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

<Example 1>
(Production of laminated film)
An inorganic layer made of silicon oxide and a layer containing amorphous carbon were sequentially formed on a 100 μm-thick PET (Toray Co., Ltd., Lumirror T60) film to produce a laminated film. Details are shown below.

1. Production of the first layer On the PET film treated with oxygen plasma, while controlling the amount of Si evaporation and the amount of oxygen gas introduced, reactive deposition is performed under vacuum to form a silicon oxide layer having a thickness of 100 nm. 1A.

2. Production of Second Layer An amorphous carbon layer having a thickness of 100 nm was formed on the silicon oxide layer of the film 1A by a plasma CVD method using methane as a raw material to obtain a film 2A. Further, a 100 nm thick UV curable resin (acrylate resin) was formed on the silicon oxide layer of the film 1A by spin coating, and this was used as a film 2B.

3. Production of third layer After the surface of the amorphous carbon layer of the film 2A is subjected to oxygen plasma treatment (conditions: plasma generation by applying a voltage at an oxygen partial pressure of 2 mTorr and a chamber pressure of 1 mTorr), the amount of Si evaporation and the amount of oxygen gas introduced While controlling the above, reactive vapor deposition was performed under vacuum to form a 100 nm-thick silicon oxide layer, which was designated as film 3A. Moreover, the silicon oxide layer was similarly formed in the state which does not surface-treat to film 2A, and this was made into film 3B. On the other hand, the film 2B is placed on a plate in a radio frequency (RF) plasma generator (BP-1, manufactured by SAMCO), and the plasma is generated at a high frequency by reducing the pressure while supplying oxygen gas. After the oxygen plasma treatment, the silicon oxide layer having a film thickness of 100 nm was formed by reacting and vapor-depositing under vacuum while controlling the amount of Si evaporation and the amount of oxygen gas introduced to obtain a film 3C. Further, a silicon oxide layer was formed in the same manner in a state where the film 2B was not subjected to surface treatment, and this was used as a film 3D.

4). Production of Transparent Conductive Layer The films 3A to 3D were introduced into a vacuum chamber, and a transparent electrode made of an ITO thin film having a thickness of 200 nm was formed by DC magnetron sputtering using an ITO target. This was made into film 4A, 4B, 4C, 4D, respectively. Moreover, the transparent conductive layer was similarly formed in the film 1A which consists only of the inorganic layer of the 1st layer, and this was made into the film 4E.

<Test Example 1>
(Measurement of number of oxygen atoms / number of carbon atoms)
The ratio of (number of oxygen atoms / number of carbon atoms) on the surface of the amorphous carbon layer of films 4A and 4B and the number of (oxygen atoms / number of carbon atoms) on the surface of the amorphous carbon layer or the UV curable resin layer in films 4C and 4D. The ratio was measured by the XPS method. Using a PHI 1600S X-ray photoelectron spectrometer and etching the surface of the film by argon ion sputtering from the surface of the film, the silica component disappears after the top ITO layer, and an amorphous carbon layer or UV curable resin layer is formed. appear. The determination of the amorphous carbon layer or the UV curable resin layer can be confirmed when a carbon component appears. In the amorphous carbon layer, a carbon component and an oxygen component appear at the same time when oxygen plasma treatment is performed, and a layer containing only the carbon component appears later. On the other hand, the amorphous carbon layer not subjected to the oxygen plasma treatment shows that the oxygen component does not appear and the surface of the amorphous carbon layer is not oxidized. Further, in the UV curable resin layer, an oxygen component always exists in the depth direction, and a layer containing only a carbon component does not exist. Therefore, the ratio of the number of oxygen atoms to the number of carbon atoms (the number of oxygen atoms / the number of carbon atoms) is calculated from the C1s and O1s peak areas of C—O and C═O bonds in a region where the carbon component and oxygen component of the amorphous carbon layer coexist. did. The results are shown in Table 1.

<Test Example 2>
(Measurement of gas barrier properties)
According to the present invention and comparative films 4A to 4E, the oxygen transmission rate at 38 ° C./relative humidity 10% and 90% and the water vapor transmission rate at 38 ° C./relative humidity 90% were measured using the MOCON method (oxygen: MOCON OX-TRAN 2/20 L, water vapor: measured by MOCON PERMATRAN-W (3) / 31). The results are shown in Table 2.

<Test Example 3>
(Bending test)
Each of the films 4A to 4E is cut into 20 cm × 30 cm, and both ends are bonded to form a columnar shape with the gas barrier coat layer on the outside. Then, two 12 mmφ transfer rollers are applied with a tension of about 1 N between the two rollers, and the film The film was rotated and conveyed at 30 cm / min while paying attention so that the roller part and the roller part completely contacted and the film did not slip. Each film was conditioned for 8 hours in an environment of 25 ° C. and a relative humidity of 60%, and then tested in a laboratory under the same conditions. After the above operation, gas barrier properties were measured in the same manner as in Test Example 1. The results are shown in Table 3.

<Test Example 4>
(Heat resistance test)
The surface of the barrier coating layer of each of the films 4A to 4E was irradiated with a commercially available infrared heater until the surface temperature rose to 150 ° C, and then cooled to 25 ° C. Done in the same way. The surface temperature was monitored with a commercially available radiation thermometer. The results are shown in Table 4.

<Test Example 5>
(Adhesion test)
In order to evaluate the adhesion of the laminated film, a cross-cut test based on JIS K5400 was performed. Cuts of 90 ° with respect to the film surface were made at 1 mm intervals on the surfaces of the films 3A to 3D with a cutter knife, and 100 grids with 1 mm intervals were produced. A 2 cm wide Mylar tape was affixed thereon, and the tape affixed using a tape peeling tester was peeled off. Of the 100 grids on the film, the number of cells remaining without peeling was counted and evaluated. The results are shown in Table 5.

From Table 2, the gas barrier property of the present invention in which an inorganic layer and an amorphous carbon layer are laminated and the amorphous carbon layer is subjected to surface treatment so that the ratio of (number of oxygen atoms / number of carbon atoms) falls within the scope of the present invention. The laminated film is a film 4C, 4D having a layer of UV curable resin between two inorganic layers, or a film 4E having no inorganic carbon layer and only one inorganic layer on the support, It can be seen that the oxygen transmission rate and the water vapor transmission rate are excellent. Further, as can be seen from Table 3, the film 4A of the present invention was not deteriorated in gas barrier performance due to the bending test as in the films 4B to 4E. Without being bound by any theory, this is because many functional groups containing oxygen are formed on the surface of the amorphous carbon film, increasing the affinity with the inorganic layer, and as a result, the amorphous carbon layer and the inorganic layer This is considered to be because the adhesion force was increased and the occurrence of interface peeling and cracking was suppressed. Further, as can be seen from Table 4, in the heat resistance test, the gas barrier laminate film 4A of the present invention was not deteriorated in gas barrier performance. Thus, the gas barrier laminate film of the present invention has a good gas barrier due to a synergistic effect by laminating the inorganic layer and the amorphous carbon layer and improving the ratio of (number of oxygen atoms / number of carbon atoms) of the amorphous carbon layer. It can be seen that performance is obtained.
Furthermore, it can be seen from Table 5 that the adhesion with the inorganic layer is improved by plasma treatment of the surface of the amorphous carbon. Even in the UV curable resin layer, adhesion was improved, but partly tended to peel off, and it was found that the adhesion was weaker than that of the amorphous carbon layer.

<Example 2>
(Production of substrate and organic EL device)
Aluminum lead wires were connected from the transparent electrode (ITO) of the film 4A to form a laminated structure. The surface of the transparent electrode was spin-coated with an aqueous dispersion of polyethylene dioxythiophene / polystyrenesulfonic acid (BAYER, Baytron P: solid content: 1.3% by mass). Then, it vacuum-dried at 150 degreeC for 2 hours, and formed the 100-nm-thick hole transportable organic thin film layer. This was designated as substrate X.

  On the other hand, using a spin coater, a coating solution for a light-emitting organic thin film layer having the following composition is formed on one surface of a temporary support made of polyethersulfone having a thickness of 188 μm (Sumilite FS-1300, manufactured by Sumitomo Bakelite Co., Ltd.). By coating and drying at room temperature, a light-emitting organic thin film layer having a thickness of 13 nm was formed on the temporary support. This was designated as transfer material Y.

(composition)
Polyvinylcarbazole 40 parts by mass (Mw = 63000, manufactured by Aldrich)
・ Tris (2-phenylpyridine) iridium complex 1 part by mass (orthometalated complex)
・ 1,200 parts by mass of 1,2-dichloroethane

  The luminescent organic thin film layer side of the transfer material Y is superimposed on the upper surface of the organic thin film layer of the substrate X, and heated and pressurized at 160 ° C., 0.3 MPa, 0.05 m / min using a pair of heat rollers, and a temporary support Was peeled off to form a light-emitting organic thin film layer on the upper surface of the substrate X. This was designated as substrate XY.

  A patterned mask (a mask with a light emitting area of 5 mm × 5 mm) is placed on one side of a polyimide film (UPILEX-50S, manufactured by Ube Industries) with a thickness of 50 μm cut into 25 mm square, and Al is deposited to a thickness of 250 nm by vapor deposition. Then, LiF was formed to a thickness of 3 nm by a vapor deposition method. A coating solution for an electron transporting organic thin film layer having the following composition is applied onto the obtained laminated structure using a spin coater coating machine, and vacuum dried at 80 ° C. for 2 hours, whereby an electron having a thickness of 15 nm is obtained. A transportable organic thin film layer was formed on LiF. Furthermore, an aluminum lead wire was connected from the Al electrode, and this was used as a substrate Z.

(composition)
Polyvinyl butyral 2000L 10 parts by mass (Mw = 2000, manufactured by Denki Kagaku Kogyo Co., Ltd.)
1-butanol: 3500 parts by mass Electron transporting compound having the following structure 20 parts by mass

  Using the substrates XY and Z, the electrodes are stacked so that the electrodes face each other with the light-emitting organic thin film layer interposed therebetween, and heated and pressurized at 160 ° C., 0.3 MPa, 0.05 m / min using a pair of heat rollers, The organic EL element was produced by bonding.

  A direct measure voltage was applied to the obtained organic EL device using a source measure unit 2400 type (manufactured by Toyo Technica Co., Ltd.) to emit light. The organic EL device of the present invention emitted light well. After the organic EL device was fabricated, it was allowed to stand at 25 ° C. and 10% and 90% relative humidity for 12 hours for 10 days and emitted light in the same manner, but no degradation of the device was observed.

Claims (7)

  A surface of at least one amorphous carbon layer (B) having at least one inorganic layer (A) and at least one amorphous carbon layer (B) mainly composed of amorphous carbon on a substrate film. A gas barrier laminate film, wherein the ratio of (number of oxygen atoms / number of carbon atoms) is 0.01 or more.   The ratio of (number of oxygen atoms / number of carbon atoms) on the surface of at least one amorphous carbon layer (B) is 0.01 or more due to surface treatment. 2. The gas barrier laminate film according to 1.   The gas barrier laminate film according to claim 2, wherein the surface treatment is an oxygen plasma treatment.   The gas barrier laminate film according to any one of claims 1 to 3, wherein the inorganic layer (A) layer and the amorphous carbon layer (B) are alternately laminated. The oxygen permeability at 38 ° C. and 90% relative humidity is 0.01 ml / m ² · day · atm or less, and the water vapor permeability at 38 ° C. and 90% relative humidity is 0.01 g / m ² · day or less. The gas barrier laminate film according to any one of claims 1 to 4, wherein:   The gas barrier laminate film according to any one of claims 1 to 5, wherein the gas barrier laminate film has a gas barrier property even after a bending test.   An image display element using the gas barrier laminate film according to claim 1.