JP2015024536A - Method of manufacturing gas barrier film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing a gas barrier film having excellent flatness, excellent adhesion after preserved in an environment of a high temperature and a high humidity, and good gas barrier properties.SOLUTION: The method of manufacturing a gas barrier film comprises a step A of subjecting the surface of a film substrate having a cycloolefin polymer or a cycloolefin copolymer as a main component to vacuum ultraviolet irradiation treatment thereby making the surface hydrophilic, a step B of applying a solution of a clear hard coat layer onto the hydrophilic surface of the film substrate, a step C of curing the clear hard coat layer, and a step D of forming a gas-barrier layer on the cured clear hard coat layer.

Description

  The present invention relates to a method for producing a gas barrier film, a gas barrier film, and an organic electroluminescence device having the gas barrier film. In particular, the present invention relates to a method for producing a gas barrier film that has excellent adhesion even under a high temperature and high humidity environment and can maintain high gas barrier properties.

  An organic electroluminescence element (hereinafter also referred to as an organic EL element) using an organic material electroluminescence (hereinafter abbreviated as EL) can emit light at a low voltage of about several volts to several tens of volts. It is a thin film type complete solid-state device and has many excellent features such as high brightness, high luminous efficiency, thinness, and light weight. For this reason, it has been attracting attention in recent years as surface light emitters such as backlights for various displays, display boards such as signboards and emergency lights, and illumination light sources.

  In an organic EL element using a resin base material to make it a thin, lightweight and flexible element, a gas that blocks the penetration of various gases such as water vapor and oxygen into the organic EL element inside the resin base material A barrier film may be provided. By providing the organic EL element with the gas barrier film, the influence from the external environment is blocked and the deterioration of the function of the organic EL element is suppressed.

  The flexible organic EL element can maintain its shape in a curved surface due to its characteristics. However, if such a curved surface is maintained for a long time, there is a problem that adhesion and gas barrier properties deteriorate. One of the causes is the deterioration of the gas barrier film provided on the resin base material. This is because the gas barrier film has a laminated structure in which a plurality of organic layers, inorganic layers, etc. are laminated, and the curved surface state lasts for a long time, causing cracks in specific constituent layers or between each constituent layer. It is presumed that this is because peeling occurs.

  In order to solve such a problem, in Patent Document 1, a physical vapor deposition method (PVD method), a low temperature plasma vapor deposition method, a chemical deposition method (CVD) is formed on a polyethylene terephthalate (hereinafter abbreviated as PET) substrate. And an inorganic / organic hybrid polymer layer (ORMOCER) formed by applying a silicon-based metal alkoxide or a derivative thereof, an aluminum compound and, if necessary, a compound containing another metal element. It is described that a gas barrier film with improved bending resistance can be provided by laminating a layer). The same document also proposes a gas barrier film having improved bending resistance by setting the thickness of the ORMOKER layer in the range of 0.05 to 0.95 μm.

  However, the gas barrier film described in Patent Document 1 has excellent bending resistance, but when exposed to a high temperature and high humidity environment for a long time, the metal oxide layer and the inorganic / organic hybrid polymer layer There was a problem that the adhesion between the layers was reduced and the gas barrier property was deteriorated. In addition, since polyethylene terephthalate is applied as a base material, it has problems that transparency is slightly low, birefringence (retardation value) is high, and color angle dependency is large. When a gas barrier film using terephthalate as a base material is used for an organic EL element, in addition to the above-mentioned problems such as transparency, birefringence, and visibility, the durability of the above gas barrier film There has been a problem that the light emitting performance of the organic EL element is also deteriorated due to the deterioration.

  In Patent Document 2, a gas barrier having a gas barrier layer formed by subjecting a polysilazane film formed by applying a polysilazane-containing liquid to at least one surface side of a base material, for example, a PET film, by plasma treatment. A functional film is disclosed. According to the method disclosed in Patent Document 2, it is said that a gas barrier film having excellent gas barrier properties, a short manufacturing time, and excellent substrate selectivity can be provided. As above, there is a problem that the adhesion between the base material and the gas barrier layer is not sufficient when exposed to a high temperature and high humidity environment for a long time.

  Furthermore, in Patent Document 1 and Patent Document 2, PET film or the like is mainly used as the film substrate, but PET film has the above-described transparency, birefringence, and visibility. In addition to problems such as the above, since the barrier property against moisture etc. is low, when forming a gas barrier film, it is necessary to design the gas barrier layer to be applied in order to exhibit advanced gas barrier performance. There are increasing constraints on the structure of the barrier layer.

  In response to the above problems, as a film base material for gas barrier films, in recent years, it has excellent optical properties and has a low retardation value. In particular, the moisture permeability is 0.1 times that of PET and 0.001 of a triacetyl cellulose film. A cycloolefin resin film having a moisture permeability as low as about twice has been studied. By applying a cycloolefin resin film having such characteristics as the base material of the gas barrier film, the degree of freedom in designing the gas barrier layer formed thereon can be expanded.

  However, the cycloolefin resin film has poor adhesion to a functional layer constituting a gas barrier film formed thereon. As a method for dealing with the adhesion, a method of forming a clear hard coat layer or a gas barrier layer after hydrophilization treatment, for example, corona treatment or plasma treatment on the surface of the cycloolefin resin film has been studied.

  However, in the cycloolefin resin film subjected to hydrophilic treatment by corona treatment or plasma treatment, the gas barrier film disclosed in Patent Document 1 and Patent Document 2 has a high temperature and high humidity environment as well as the problem of the gas barrier film. When stored over a long period of time, there is a problem that peeling occurs between the cycloolefin resin film and the clear hard coat layer or gas barrier layer formed thereon, and the excellent gas barrier performance gradually decreases. It has been found.

Japanese Patent Laid-Open No. 2002-046208 JP 2007-237588 A

  The present invention has been made in view of the above problems, and the solution to the problem is excellent flatness, excellent adhesion even after being stored for a long time in a high temperature and high humidity environment, and maintains high gas barrier properties. It is providing the manufacturing method of the gas-barrier film which can do.

  As a result of diligent investigations in view of the above problems, the present inventor has made the surface of a film substrate mainly composed of a cycloolefin polymer etc. hydrophilic by applying a vacuum ultraviolet irradiation treatment, and a clear hard coat layer is formed thereon. Formed by subjecting the clear hard coat layer to a curing process and forming a gas barrier layer on the clear hard coat layer. The present inventors have found that it is possible to provide a method for producing a gas barrier film that has excellent adhesion and can maintain high gas barrier properties even after being stored for a long period of time in an environment, and has led to the present invention.

  That is, the said subject of this invention is solved by the following means.

1. Step A for hydrophilizing the surface of a film substrate mainly composed of a cycloolefin polymer or a cycloolefin copolymer by subjecting it to a vacuum ultraviolet ray irradiation treatment,
Step B of forming a clear hard coat layer by applying a clear hard coat layer coating solution on the hydrophilic surface of the film base,
Step C for applying a curing treatment to the clear hard coat layer,
And Step D of forming a gas barrier layer on the cured clear hard coat layer,
A method for producing a gas barrier film, characterized by being manufactured through the process.

  2. 2. The gas according to claim 1, wherein before the step C, a step E of applying a heat resistant laminate member is provided on the surface of the film base opposite to the surface subjected to the vacuum ultraviolet irradiation treatment. A method for producing a barrier film.

  3. 3. The method for producing a gas barrier film according to item 1 or 2, wherein the gas barrier layer is formed by a chemical vapor deposition method (CVD method).

  4). 4. The method for producing a gas barrier film according to item 3, wherein the chemical vapor deposition method used for forming the gas barrier layer is a discharge plasma chemical vapor deposition method (plasma CVD method).

  5. The method for producing a gas barrier film according to any one of items 1 to 4, wherein the film substrate has a thickness in a range of 30 to 150 µm.

  6). Item 6. The method for producing a gas barrier film according to any one of Items 1 to 5, wherein the clear hard coat layer has a thickness of 1 to 10 µm.

  By the above means of the present invention, there is provided a method for producing a gas barrier film having excellent flatness, excellent adhesion even after being stored for a long time in a high temperature and high humidity environment, and capable of maintaining high gas barrier properties. can do.

  The expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.

  The present invention is characterized in that a clear hard coat layer is provided as a functional layer for adhering both between a film base material mainly composed of a cycloolefin polymer or a cycloolefin copolymer and a gas barrier layer. Conventionally, as for the surface treatment of the film base material when the clear hard coat layer is installed, a corona discharge treatment or a plasma discharge treatment is generally performed immediately before applying the clear hard coat. Since such a surface treatment is a treatment in an air atmosphere, immediately after the treatment, moisture from the treatment environment is easily adsorbed on the substrate treatment surface.

  On the other hand, in the present invention, the film substrate surface is treated with excimer light immediately before the clear hard coat is placed on the film substrate surface according to the present invention. At this time, the film substrate is dried with a very low moisture concentration. Since it is placed in a nitrogen atmosphere, it can be predicted that the surface of the film substrate immediately after the surface treatment by excimer light is in a very low moisture state. As a result, immediately after the treatment with excimer light, when the clear hard coat layer is applied, the moisture concentration in the interface region between the film substrate and the clear hard coat is kept low.

  As a result, it is considered that the film substrate mainly composed of a cycloolefin polymer or cycloolefin copolymer having poor adhesion to the clear hard coat layer contributes to maintaining adhesion during storage.

  In the present invention, a step of applying a heat-resistant laminate member is provided before the clear hard coat layer is cured. This suppresses surface unevenness that occurs when the clear hard coat layer is cured. Then, it is thought that it contributes to the improvement of adhesiveness with the gas barrier layer formed in the present invention and the maintenance of performance when stored for a long time in a high temperature and high humidity environment. In addition, it is thought that the surface unevenness here refers to the height of the linear thermal expansion coefficient of the film base material according to the present invention and the heat generated when the clear hard coat is cured.

Schematic sectional view showing an example of the configuration of the gas barrier film of the present invention Schematic which shows an example of the process flow applicable to the manufacturing method of the gas barrier film of this invention Schematic diagram showing an example of a vacuum ultraviolet irradiation apparatus applicable to the present invention Graph showing silicon distribution curve, oxygen distribution curve and carbon distribution curve in gas barrier layer The graph which expanded the carbon distribution curve shown in FIG. Graph showing refractive index distribution of gas barrier layer The schematic diagram which shows an example of the discharge plasma processing apparatus suitable for formation of the gas barrier layer based on this invention The schematic block diagram which shows an example of a structure of the organic EL element which comprised the gas barrier film of this invention

  The method for producing a gas barrier film of the present invention comprises the step A of hydrophilizing the surface of a film substrate mainly comprising a cycloolefin polymer or a cycloolefin copolymer by subjecting it to a vacuum ultraviolet irradiation treatment, the hydrophilicity of the film substrate. Step B for forming a clear hard coat layer by applying a clear hard coat layer coating solution on the converted surface, Step C for subjecting the clear hard coat layer to a curing treatment, Gas barrier on the cured clear hard coat layer It manufactures through the process D of forming a layer, It is characterized by the above-mentioned. This feature is a technical feature common to the inventions according to claims 1 to 8.

  As an embodiment of the present invention, from the viewpoint of more manifesting the intended effect of the present invention, before the step C for performing the curing treatment, the side opposite to the surface subjected to the vacuum ultraviolet irradiation treatment of the film substrate is used. It is possible to provide the surface with a process E for applying a heat-resistant laminate member. For example, even if the film substrate is exposed to a high heat environment after the process C, a gas barrier excellent in flatness without causing thermal deformation or the like. From the viewpoint of obtaining a conductive film.

  In Step D, a chemical vapor deposition method (CVD method) is applied as a method for forming a gas barrier layer, and a discharge plasma chemical vapor deposition method is applied as a chemical vapor deposition method. From the viewpoint that the gas barrier layer can be formed with a desired composition and the element distribution in the layer can be precisely controlled.

  Moreover, by setting it as the structure of this invention, high moisture-permeation tolerance can be implement | achieved, As a result, the film thickness of a film base material can be in the range of 30-150 micrometers, and it is thinned and gasses A barrier film can be obtained.

  Similarly, after the surface of the film substrate is hydrophilized by vacuum ultraviolet irradiation treatment, the adhesion between the film substrate and the clear hard coat layer is improved by forming a clear hard coat layer. The thickness of the hard coat layer can be in the range of 1 to 10 μm, and a gas barrier film can be obtained by thinning.

  By providing the organic electroluminescent device with a gas barrier film obtained by the production method of the present invention, durability (interlayer adhesion) is improved, even after being stored for a long period under high temperature and high humidity, For example, the occurrence of dark spots can be suppressed.

  Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In addition, "-" shown in the following description is used with the meaning which includes the numerical value described before and behind that as a lower limit and an upper limit.

<Gas barrier film>
FIG. 1 is a schematic cross-sectional view showing an example of the configuration of the gas barrier film of the present invention.

  As shown in FIG. 1, the gas barrier film 1 of the present invention is subjected to a surface modification treatment by vacuum ultraviolet irradiation treatment on one surface side of a film substrate 2 mainly composed of a cycloolefin polymer or a cycloolefin copolymer. It has a surface modification region 3 applied. A clear hard coat layer 4 and a gas barrier layer 5 are laminated on the surface modification region 3 to constitute a gas barrier film 1.

In addition, the heat-resistant laminate member 6 is applied to the surface of the film base 2 opposite to the surface subjected to the surface modification treatment by the vacuum ultraviolet irradiation treatment until the clear hard coat layer is cured. Has been. Process A to Process D
<< Method for producing gas barrier film >>
The gas barrier film of the present invention is basically produced through the following steps A to D.

Step A: A step of hydrophilizing the surface of a film substrate mainly composed of a cycloolefin polymer or a cycloolefin copolymer by subjecting it to a vacuum ultraviolet ray irradiation treatment,
Step B: A step of forming a clear hard coat layer by applying a clear hard coat layer coating solution on the hydrophilic surface of the film base,
Step C: a step of applying a curing treatment to the clear hard coat layer,
Step D: A step of forming a gas barrier layer on the cured clear hard coat layer.

  Further, in addition to the steps A to D, a configuration in which, before the step C, a step E of applying a heat-resistant laminate member to the surface of the film base opposite to the surface subjected to the vacuum ultraviolet irradiation treatment is provided. preferable.

  The outline | summary of the manufacturing method of the gas barrier film of this invention is demonstrated using a figure.

  FIG. 2 is a schematic view showing an example of a process flow applicable to the method for producing a gas barrier film of the present invention.

  In (1) of FIG. 2, the film base material 2 which has a cycloolefin polymer or a cycloolefin copolymer as a main component as a film base material 2 is prepared.

  Subsequently, before the surface modification treatment by excimer light is performed on the surface of the film base 2, the surface modification region 3 is formed on the film base 2 in the next step in the step E shown in FIG. A heat-resistant laminate member 6 excellent in heat resistance is imparted to a surface opposite to the surface to be performed (also referred to as a back surface), and resistance to thermal energy imparted in subsequent steps is imparted.

  Next, in step A shown in (3) of FIG. 2, a vacuum ultraviolet ray irradiation device (excimer light irradiation) is applied to the surface side (also referred to as surface) of the film base 2 opposite to the surface to which the heat resistant laminate member 6 is applied. The surface modification region 3 is formed by irradiating the excimer light L using an apparatus 7 and performing surface modification treatment (hydrophilization treatment).

  Although details of the excimer light irradiation device 7 will be described later, the excimer lamp 9 is configured by an excimer lamp 9 and a holder 8 for holding the excimer lamp, and the excimer lamp 9 is applied to emit excimer light L having a wavelength of 172 nm.

  In the present invention, from the viewpoint of increasing the efficiency of the vacuum ultraviolet irradiation treatment, the vacuum ultraviolet irradiation treatment in the step A is preferably performed in an environment where the influence of oxygen is blocked, such as a vacuum environment or a nitrogen atmosphere.

  Subsequently, in step B shown in FIG. 2 (4), a clear hard coat layer (uncured) 4 A is applied on the surface modified region 3. Although there is no restriction | limiting in particular as a formation method of a clear hard-coat layer, The method of apply | coating and drying by a wet application system using the coating liquid for clear hard-coat layer formation is preferable.

  Next, in the process C shown in FIG. 2 (5), the clear hard coat layer (uncured) 4A formed as described above is subjected to a curing process. For example, when the clear hard coat layer (uncured) 4A is formed of a thermosetting resin, the curing means 10 is cured by applying thermal energy using a heater or the like. Alternatively, when the clear hard coat layer (uncured) 4A is formed of an actinic ray (for example, ultraviolet ray) curable resin, the curing means 10 is cured by irradiating ultraviolet rays or the like using an ultraviolet irradiation device or the like. Then, the clear hard coat layer 4 is formed.

  Finally, in step D shown in FIG. 2 (6), the gas barrier layer 5 is formed on the formed clear hard coat layer 4 to produce the gas barrier film 1.

  As a method for forming the gas barrier layer 5, a vapor deposition method or a wet coating method (for example, a method in which perhydroxypolysilazane (PHPS) is used to modify by vacuum ultraviolet irradiation treatment) or the like can be applied. Applying a chemical vapor deposition method (CVD method), or applying a discharge plasma chemical vapor deposition method (plasma CVD method) as a chemical vapor deposition method, the gas barrier layer has a desired composition. And the element distribution in the layer can be precisely controlled.

  Details of the plasma CVD method and the like will be described later.

<Each component of gas barrier film>
[Film base]
In the gas barrier film of the present invention, a film substrate mainly composed of a cycloolefin polymer (hereinafter also referred to as COP) or a cycloolefin copolymer (hereinafter also referred to as COC) is applied as the substrate. Features.

  The term “main component” as used in the present invention means that, among the resin components constituting the film substrate, the constituent ratio of COP and COC is 60% by mass or more, preferably 80% by mass or more, More preferably, it is 90 mass% or more, Most preferably, it is comprised by 95 mass% or more.

  The film substrate formed of the cycloolefin polymer or cycloolefin copolymer according to the present invention has a relatively low moisture permeability and superior light transmittance as compared with a polyethylene terephthalate film that has been widely used conventionally. (Transparency), and when it is provided in an organic EL element, it has a feature that luminous efficiency is improved. Furthermore, the birefringence is low, and when the organic EL device is provided, the color viewing angle dependency is small.

  In general, since it is difficult to homopolymerize a cyclic olefin due to the influence of steric hindrance, etc., there are two methods, a method A for addition polymerization with α-olefin and the like and a method B by ring-opening polymerization of a cyclic olefin. The polymer of the method A is called a cycloolefin copolymer (COC), and the polymer of the latter method B is called a cycloolefin polymer (COP).

  The cycloolefin polymer applicable to the present invention is a polymer resin containing an alicyclic structure. A preferred cycloolefin polymer is a resin obtained by polymerizing or copolymerizing a cyclic olefin. Examples of the cyclic olefin include norbornene, dicyclopentadiene, tetracyclododecene, ethyltetracyclododecene, ethylidenetetracyclododecene, tetracyclo [7.4.0.110, 13.02,7] trideca-2, Polycyclic unsaturated hydrocarbons such as 4,6,11-tetraene and derivatives thereof; cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene , Cyclooctene, 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene, unsaturated hydrocarbon having a monocyclic structure such as cycloheptene, cyclopentadiene, cyclohexadiene, and derivatives thereof. These cyclic olefins may have a polar group as a substituent. Examples of the polar group include a hydroxy group, a carboxy group, an alkoxyl group, an epoxy group, a glycidyl group, an oxycarbonyl group, a carbonyl group, an amino group, an ester group, and a carboxylic acid anhydride group. A carboxy group or a carboxylic anhydride group is preferred.

  A preferred cycloolefin polymer may be a cycloolefin copolymer obtained by addition copolymerization of a monomer other than a cyclic olefin. Examples of the addition copolymerizable monomer include ethylene or α-olefin such as ethylene, propylene, 1-butene and 1-pentene; 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5- And dienes such as methyl-1,4-hexadiene and 1,7-octadiene.

  The cyclic olefin can be obtained by an addition polymerization reaction or a metathesis ring-opening polymerization reaction. The polymerization reaction is usually performed in the presence of a catalyst.

  The cycloolefin polymer is preferably a polymer obtained by polymerizing or copolymerizing a cyclic olefin, followed by hydrogenation reaction to convert unsaturated bonds in the molecule into saturated bonds. The hydrogenation reaction is performed by blowing hydrogen in the presence of a known hydrogenation catalyst.

  Moreover, the following norbornene-type resin is also mentioned as a cycloolefin polymer. The norbornene-based resin preferably has a norbornene skeleton as a repeating unit. Specific examples thereof include, for example, JP-A-62-252406, JP-A-62-2252407, and JP-A-2-133413. JP, 63-145324, 63-264626, 63-240517, 57-81515, 5-2108, and 5-39403. JP-A-5-43663, JP-A-5-43834, JP-A-5-70655, JP-A-5-279554, JP-A-6-206985, JP-A-7-62028. JP-A-8-176411, JP-A-9-241484, JP-A-2001-277430, JP-A-2003-13. 950, JP2003-14901, JP2003-161832, JP2003-195268, JP2003-111588, JP2003-211589, JP2003-268187 Gazette, JP-A-2004-133209, JP-A-2004-309799, JP-A-2005-121183, JP-A-2005-164632, JP-A-2006-72309, JP-A-2006-178191, Although what was described in Unexamined-Japanese-Patent No. 2006-215333, Unexamined-Japanese-Patent No. 2006-268065, Unexamined-Japanese-Patent No. 2006-299199 etc. is mentioned, It is not limited to these. Moreover, these may be used independently and may use 2 or more types together.

  The cycloolefin polymer according to the present invention can be obtained as a commercially available product, for example, Essina (trade name) manufactured by Sekisui Chemical Co., Ltd., ZEONEX, ZEONOR (trade name) manufactured by ZEON CORPORATION, Artron (trade name) manufactured by JSR Corporation, Optretz (trade name) manufactured by Hitachi Chemical Co., Ltd., Appell (trade names, APL8008T, APL6509T, APL6013T, APL5014DP, APL6015T) manufactured by Mitsui Chemicals, Inc. are preferably used. .

  As a method for producing a COP film or COC film according to the present invention, a production method such as a normal inflation method, a T-die method, a calendar method, a cutting method, a casting method, an emulsion method, or a hot press method can be used. A conventionally known solution casting film forming method or melt casting film forming method can be selected as the film forming method.

[Surface treatment of film substrate]
The COP film or COC film which is the film substrate according to the present invention has excellent optical properties as described above, but the adhesion to the constituent layer formed on the substrate is not sufficient, and the adhesion It was an important technical issue.

  Conventionally, surface treatments such as corona treatment and plasma treatment have been performed for the purpose of improving the adhesion of COP films and the like, and functional layers such as a smooth layer, a clear hard coat layer, or a gas barrier have been provided thereon. When a gas barrier film is prepared by coating layers and the gas barrier film is stored for a long period of time in a high-temperature and high-humidity environment, there is a problem that film separation occurs between the COP film surface and the constituent layers. It has been found.

  As a result of proceeding with improved technologies including verification of various technical mechanisms, the COP substrate surface was subjected to vacuum ultraviolet irradiation treatment as a hydrophilization treatment, and then a clear hard coat layer was formed thereon. By forming, high adhesion as a gas barrier film could be realized.

  The reason why excellent adhesion can be obtained by subjecting the surface of the film substrate formed by the cycloolefin polymer or cycloolefin copolymer, which is a feature of the present invention, to vacuum ultraviolet irradiation is presumed as follows. doing.

  That is, as described above, when performing a corona discharge treatment or a plasma discharge treatment, most of the treatment is performed in an air atmosphere. It affects the adhesion deterioration between the film substrate formed of the olefin polymer or the cycloolefin copolymer and the clear hard coat layer. In contrast, in the present invention, immediately before the clear hard coat layer is formed on the surface of the film substrate formed of the cycloolefin polymer or the cycloolefin copolymer, the surface of the film substrate is treated with excimer light. Although it is characterized, in this treatment with excimer light, since the film substrate according to the present invention is performed in a dry nitrogen atmosphere with a very low moisture concentration, the film substrate surface according to the present invention immediately after the surface treatment with excimer light is It is in a very low moisture state. As a result, the interface region between the clear hard coat layer and the film substrate that is formed immediately after is maintained at a low moisture concentration. As a result, in particular, the cycloolefin polymer or cycloolefin having poor adhesion to the clear hard coat layer. In the film base material which has a copolymer as a main component, it is thought that it contributes to the adhesiveness maintenance at the time of a preservation | save.

(Vacuum ultraviolet irradiation treatment: excimer light irradiation treatment)
As a vacuum ultraviolet irradiation treatment according to the present invention, a surface treatment method using excimer light irradiation treatment is a preferred embodiment. Hereinafter, the details of the vacuum ultraviolet irradiation treatment applicable to the present invention will be described.

  The hydrophilic treatment of the film substrate surface by vacuum ultraviolet irradiation applicable to the present invention uses light energy having an emission wavelength of 100 to 200 nm, preferably using energy of light having a wavelength of 100 to 180 nm to bond atoms. This is a method of performing hydrophilic treatment on the surface of a film substrate at a relatively low temperature by the action of only photons called a photon process.

In vacuum ultraviolet ray irradiation treatment in the present invention, it is preferable that the illuminance of the vacuum ultraviolet rays in the film base surface (excimer light) is in the range of 30~200mW / cm ^2, in the range of 50~160mW / cm ² More preferred. If it is 30 mW / cm ² or more, the surface modification effect (hydrophilization effect) by excimer light can be repelled, and if it is 200 mW / cm ² or less, the film substrate is not damaged, which is preferable.

Further, the accumulated amount of the VUV in the film substrate surface, is preferably in the range of 200~10000mJ / cm ^2, and more preferably in the range of 500~5000mJ / cm ^2. If it is this range, the surface hydrophilization treatment effect is sufficient and the thermal deformation of the film substrate does not occur.

  As the vacuum ultraviolet light source, a rare gas excimer lamp is preferably used. Atoms of noble gases such as Xe, Kr, Ar, and Ne are called inert gases because they are not chemically bonded to form molecules.

However, excited atoms of rare gases that have gained energy by discharge or the like can form molecules by combining with other atoms. When the rare gas is xenon,
e + Xe → Xe ^*
Xe ^* + 2Xe → Xe ₂ ^* + Xe
Xe ₂ ^* → Xe + Xe + hν (172 nm)
Thus, when the excited excimer molecule Xe ₂ ^* transitions to the ground state, excimer light of 172 nm is emitted.

  A feature of the excimer lamp is that the surface modification efficiency is high because radiation concentrates on one wavelength and almost no light other than necessary is emitted. Further, since no extra light is emitted, the temperature of the object can be kept low. Furthermore, since no time is required for starting and restarting, instantaneous lighting and blinking are possible.

  In order to obtain excimer light emission, a method using dielectric barrier discharge is known. Dielectric barrier discharge is a very similar to lightning that occurs in a gas space by arranging a gas space between both electrodes through a dielectric such as transparent quartz and applying a high frequency high voltage of several tens of kHz to the electrode. It is a discharge called a thin micro discharge. When the micro discharge streamer reaches the tube wall (derivative), the electric charge is accumulated on the dielectric surface, and the micro discharge disappears.

  This micro discharge spreads over the entire tube wall and repeats generation and extinction. For this reason, flickering of light that can be confirmed with the naked eye occurs. Moreover, since a very high temperature streamer reaches a pipe wall directly locally, there is a possibility that deterioration of the pipe wall may be accelerated.

  As a method for efficiently obtaining excimer light emission, electrodeless electric field discharge is possible in addition to dielectric barrier discharge. Electrodeless electric field discharge by capacitive coupling, also called RF discharge. The lamp, the electrode, and the arrangement thereof may be basically the same as those of the dielectric barrier discharge, but the high frequency applied between the two electrodes is lit at several MHz. Since the electrodeless field discharge can provide a spatially and temporally uniform discharge in this way, a long-life lamp without flickering can be obtained.

  In the case of dielectric barrier discharge, microdischarge occurs only between the electrodes, so the outer electrode covers the entire outer surface and allows light to pass through to extract light to the outside in order to cause discharge throughout the discharge space. Must be a thing.

  For this reason, an electrode in which a fine metal wire is formed in a net shape is used. Since this electrode uses as thin a line as possible so as not to block light, it is easily damaged by ozone generated by vacuum ultraviolet light in an oxygen atmosphere.

  In order to prevent this, it is necessary to provide an atmosphere of an inert gas such as nitrogen around the lamp, that is, the inside of the irradiation apparatus, and provide a synthetic quartz window to extract the irradiation light. Synthetic quartz windows are not only expensive consumables, but also cause light loss.

  Since the double cylindrical lamp has an outer diameter of about 25 mm, the difference in distance to the irradiation surface cannot be ignored between the position directly below the lamp axis and the side surface of the lamp, resulting in a large difference in illuminance. Therefore, even if the lamps are closely arranged, a uniform illuminance distribution cannot be obtained. If the irradiation device is provided with a synthetic quartz window, the distance in the oxygen atmosphere can be made uniform, and a uniform illuminance distribution can be obtained.

  When electrodeless field discharge is used, it is not necessary to make the external electrodes mesh. The glow discharge spreads over the entire discharge space simply by providing an external electrode on a part of the outer surface of the lamp. As the external electrode, an electrode that also serves as a light reflector made of an aluminum block is usually used on the back of the lamp. However, since the outer diameter of the lamp is as large as in the case of the dielectric barrier discharge, synthetic quartz is required to obtain a uniform illuminance distribution.

  The biggest feature of the capillary excimer lamp is its simple structure. The quartz tube is closed at both ends, and only gas for excimer light emission is sealed inside.

  The outer diameter of the tube of the thin tube excimer lamp is about 6 to 12 mm, and if it is too thick, a high voltage is required for starting.

  As the form of discharge, both dielectric barrier discharge and electrodeless field discharge can be used. The electrode may have a flat surface in contact with the lamp, but if the shape is matched to the curved surface of the lamp, the lamp can be firmly fixed, and the discharge is more stable when the electrode is in close contact with the lamp. Also, if the curved surface is made into a mirror surface with aluminum, it also becomes a light reflector.

  The Xe excimer lamp emits ultraviolet light having a short wavelength of 172 nm at a single wavelength, and thus has excellent luminous efficiency. Since this light has a large oxygen absorption coefficient, it can generate radical oxygen atom species and ozone at a high concentration with a very small amount of oxygen.

  In addition, it is known that the energy of light having a short wavelength of 172 nm for dissociating the bonds of organic substances has high ability. Due to the high energy of the active oxygen, ozone and ultraviolet radiation, the coating film containing polysilazane can be modified in a short time. Therefore, compared to low-pressure mercury lamps with wavelengths of 185 nm and 254 nm and plasma cleaning, it is possible to shorten the process time associated with high throughput, reduce the equipment area, and irradiate organic materials and plastic substrates that are easily damaged by heat. .

  Since the excimer lamp has high light generation efficiency, it can be turned on with low power. In addition, light having a long wavelength that causes a temperature increase due to light is not emitted, and energy is irradiated in the ultraviolet region, that is, in a short wavelength, so that the increase in the surface temperature of the target object is suppressed. For this reason, it is suitable for flexible film materials such as COP which are considered to be easily affected by heat.

  Oxygen is required for the reaction at the time of ultraviolet irradiation, but since vacuum ultraviolet rays are absorbed by oxygen, the efficiency in the ultraviolet irradiation process tends to decrease. It is preferable to carry out in a low state. That is, the oxygen concentration during vacuum ultraviolet irradiation is preferably in the range of 10 to 10000 ppm, more preferably in the range of 50 to 5000 ppm, and still more preferably in the range of 1000 to 4500 ppm.

  As a gas that satisfies the irradiation atmosphere used at the time of irradiation with vacuum ultraviolet rays, a dry inert gas is preferable, and a dry nitrogen gas is particularly preferable from the viewpoint of cost. The oxygen concentration can be adjusted by measuring the flow rate of oxygen gas and inert gas introduced into the irradiation chamber and changing the flow rate ratio.

  Next, a surface treatment method using vacuum ultraviolet irradiation treatment (excimer light irradiation treatment) will be described with reference to the drawings.

  FIG. 3 is a schematic diagram showing an example of a vacuum ultraviolet irradiation apparatus applicable to the present invention.

  The vacuum ultraviolet irradiation apparatus 7 shown in FIG. 3 is the vacuum ultraviolet irradiation apparatus 7 used in the process A described in 2) of FIG. 2 described above.

  In the vacuum ultraviolet irradiation apparatus 7 shown in FIG. 3, reference numeral 201 denotes an apparatus chamber, which is supplied with appropriate amounts of nitrogen and oxygen from a gas supply port (not shown) and exhausted from a gas discharge port (not shown). Thus, water vapor can be removed and the oxygen concentration can be maintained at a predetermined concentration. Reference numeral 9 denotes a Xe excimer lamp having a double tube structure that irradiates vacuum ultraviolet rays of 172 nm, and reference numeral 8 denotes an excimer lamp holder that also serves as an external electrode. Reference numeral 204 denotes a sample stage. The sample stage 204 can be reciprocated horizontally at a predetermined speed in the apparatus chamber 201 by a moving means (not shown). The sample stage 204 can be maintained at a predetermined temperature by a heating means (not shown). 2 is a film substrate formed of a cycloolefin polymer or a cycloolefin copolymer. When the sample stage 204 moves horizontally, the height of the sample stage 204 is adjusted so that the shortest distance between the surface of the film substrate 2 that is the sample and the tube surface of the excimer lamp 9 is 3 mm. Reference numeral 206 denotes a light shielding plate that prevents the vacuum ultraviolet light from being irradiated onto the surface of the film substrate 2 during the aging of the Xe excimer lamp 9.

  The energy applied to the surface of the film substrate 2 in the vacuum ultraviolet irradiation process was measured using a 172 nm sensor head using an ultraviolet integrated light meter: C8026 / H8025 UV POWER METER manufactured by Hamamatsu Photonics. In the measurement, the sensor head is placed in the center of the sample stage 204 so that the shortest distance between the tube surface of the Xe excimer lamp 9 and the measurement surface of the sensor head is 3 mm, and the atmosphere in the apparatus chamber 201 is Nitrogen and oxygen are supplied so that the oxygen concentration is the same as that in the vacuum ultraviolet irradiation step, and the sample stage 204 is moved at a speed V of 0.5 m / min for measurement. Prior to measurement, in order to stabilize the illuminance of the Xe excimer lamp 9, it is preferable to provide an aging time of 10 minutes after the Xe excimer lamp is turned on, and then start the measurement by moving the sample stage.

Based on the irradiation energy obtained by this measurement, the moving energy of the sample stage 204 is adjusted to adjust the irradiation energy to 6000 mJ / cm ² .

[Clear hard coat layer]
In the gas barrier film of the present invention, as shown in FIG. 1, the clear hard coat layer 4 is formed on the film substrate 2 on which the surface modified region 3 is formed by subjecting the surface to vacuum ultraviolet irradiation treatment by the above method. It is characterized by forming.

  Examples of the curable resin used for the formation of the clear hard coat layer according to the present invention include a thermosetting resin and an active energy ray curable resin. It can be preferably used.

(Thermosetting resin)
The thermosetting resin is not particularly limited. Specifically, various thermosetting resins such as epoxy resin, cyanate ester resin, phenol resin, bismaleimide-triazine resin, polyimide resin, acrylic resin, and vinylbenzyl resin can be used. Can be mentioned.

  As an epoxy resin, those having an average of two or more epoxy groups per molecule may be used. Specifically, bisphenol A type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, and naphthol type epoxy are used. Resin, naphthalene type epoxy resin, bisphenol F type epoxy resin, phosphorus-containing epoxy resin, bisphenol S type epoxy resin, aromatic glycidylamine type epoxy resin (specifically, tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, Diglycidyl toluidine, diglycidyl aniline, etc.), alicyclic epoxy resin, aliphatic chain epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin Epoxy resin having butadiene structure, phenol aralkyl type epoxy resin, epoxy resin having dicyclopentadiene structure, diglycidyl etherified product of bisphenol, diglycidyl etherified product of naphthalenediol, glycidyl etherified product of phenol, and diglycidyl alcohol Examples include etherified products, and alkyl-substituted products, halides, and hydrogenated products of these epoxy resins. These may be used alone or in combination of two or more.

(Active energy ray-curable resin)
The active energy ray-curable resin that can be suitably used in the present invention refers to a resin that cures through a crosslinking reaction or the like by irradiation with active rays such as ultraviolet rays and electron beams. As the active energy ray curable resin, a component containing a monomer having an ethylenically unsaturated double bond is preferably used. The active energy ray curable resin is cured by irradiation with an active ray such as an ultraviolet ray or an electron beam. A resin layer is formed. Typical examples of the active energy ray curable resin include an ultraviolet curable resin and an electron beam curable flag resin, but an ultraviolet curable resin that is cured by ultraviolet irradiation is preferable.

<UV curable resin>
The ultraviolet curable resin suitable for forming the clear hard coat layer according to the present invention will be described below.

  Examples of the ultraviolet curable resin include an ultraviolet curable urethane acrylate resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, and an ultraviolet curable epoxy resin. be able to.

  UV curable acrylic urethane resins generally have a hydroxyl group such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and the like obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer. It can be easily obtained by reacting an acrylate monomer having For example, a resin described in JP-A-59-151110 can be used.

  Examples of UV curable polyester acrylate resins include those which are easily formed when 2-hydroxyethyl acrylate and 2-hydroxy acrylate monomers are generally reacted with polyester polyols. JP-A-59-151112 Can be used.

  Specific examples of the ultraviolet curable epoxy acrylate resin include an epoxy acrylate as an oligomer, a reactive diluent and a photoreaction initiator added to the oligomer, and a reaction. Those described in US Pat. No. 105738 can be used.

  Further, in the present invention, it is preferable to use an ultraviolet curable polyol acrylate resin, and examples of such a compound include a polyfunctional acrylate resin. Here, the polyfunctional acrylate resin is a compound having two or more acryloyloxy groups or methacryloyloxy groups in the molecule.

  Examples of the monomer of the polyfunctional acrylate resin include ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, and tetramethylolmethane. Triacrylate, tetramethylolmethane tetraacrylate, pentaglycerol triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, glycerin triacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate , Dipen Erythritol hexaacrylate, tris (acryloyloxyethyl) isocyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, tetra Methylol methane trimethacrylate, tetramethylol methane tetramethacrylate, pentaglycerol trimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, glycerol trimethacrylate, dipentaerythritol trimethacrylate, dipentaerythritol te La methacrylate, dipentaerythritol penta methacrylate, dipentaerythritol hexa methacrylate. These compounds are used alone or in admixture of two or more. Moreover, oligomers, such as a dimer and a trimer of the said monomer, may be sufficient.

  Examples of commercially available ultraviolet curable resins applicable in the present invention include, for example, Adekaoptomer KR / BY series: KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B ( Asahi Denka Co., Ltd.); Koei Hard A-101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T-102, D-102, NS-101, FT-102Q8, MAG-1-P20, AG-106, M-101-C (manufactured by Guangei Chemical Co., Ltd.); Seika Beam PHC2210 (S), PHC X-9 (K -3), PHC2213, DP-10, DP-20, DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900 ( As described above, manufactured by Daiichi Seika Kogyo Co., Ltd.); KRM7033, KRM7039, KRM7130, KRM7131, UVECRYL29201, UVECRYL29202 (above, manufactured by Daicel UCB); RC-5015, RC-5016, RC-5020, RC- 5031, RC-5100, RC-5102, RC-5120, RC-5122, RC-5152, RC-5171, RC-5180, RC-5181 (above, manufactured by DIC Corporation); 340 clear (above, manufactured by China Paint Co., Ltd.); Sunrad H-601, RC-750, RC-700, RC-600, RC-500, RC-611, RC-612 (above, Sanyo Chemical Industries, Ltd.) SP-1509, SP-1507 (above, Showa Polymer Co., Ltd.); RCC-15C (Grace Japan, Inc.), Aronix M-6100, M-8030, M-8060 (above, Toagosei Co., Ltd.) can be selected as appropriate.

<Photopolymerization initiator>
Moreover, it is preferable to contain a photoinitiator in the range of 2-30 mass% with respect to an ultraviolet curable resin in order to accelerate | stimulate hardening of an ultraviolet curable resin. As the photopolymerization initiator, a group of double salts of onium salts that release a Lewis acid that initiates cationic polymerization by light irradiation is particularly preferable.

  As such an onium salt, it is particularly effective to use an aromatic onium salt as a cationic polymerization initiator, and among them, aromatic haloniums described in JP-A Nos. 50-151996, 50-158680, etc. Salts, group VIA aromatic onium salts described in JP-A-50-151997, 52-30899, 59-55420, 55-125105, JP-A-56-8428, 56-149402 And oxosulfonium salts described in JP-A Nos. 57-192429, aromatic diazonium salts described in JP-B No. 49-17040, and thiopyrylium salts described in US Pat. No. 4,139,655 are preferred. Moreover, an aluminum complex, a photodegradable silicon compound type | system | group polymerization initiator, etc. can be mentioned. The cationic polymerization initiator can be used in combination with a photosensitizer such as benzophenone, benzoin isopropyl ether, or thioxanthone.

<Various additives>
Further, the clear hard coat layer may contain fine particles of an inorganic compound or an organic compound in order to adjust the scratch resistance, slipperiness and refractive index.

  Inorganic fine particles used in the clear hard coat layer include silicon oxide, titanium oxide, aluminum oxide, tin oxide, indium oxide, ITO, zinc oxide, zirconium oxide, magnesium oxide, calcium carbonate, calcium carbonate, talc, clay, and firing. Mention may be made of kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate. In particular, silicon oxide, titanium oxide, aluminum oxide, zirconium oxide, magnesium oxide and the like are preferably used.

  Organic particles include polymethacrylic acid methyl acrylate resin powder, acrylic styrene resin powder, polymethyl methacrylate resin powder, silicone resin powder, polystyrene resin powder, polycarbonate resin powder, benzoguanamine resin powder, melamine resin. An ultraviolet curable resin composition such as powder, polyolefin resin powder, polyester resin powder, polyamide resin powder, polyimide resin powder, or polyfluoroethylene resin powder can be added. Particularly preferred are cross-linked polystyrene particles (for example, SX-130H, SX-200H, SX-350H, manufactured by Soken Chemical), polymethyl methacrylate-based particles (for example, MX150, MX300, manufactured by Soken Chemical), and fluorine-containing acrylic resin fine particles. . Examples of the fluorine-containing acrylic resin fine particles include commercial products such as FS-701 manufactured by Nippon Paint. Examples of the acrylic particles include Nippon Paint: S-4000, and examples of the acrylic-styrene particles include Nippon Paint: S-1200, MG-251.

  Moreover, in order to improve the heat resistance of a clear hard-coat layer, the antioxidant which does not suppress photocuring reaction can be selected and used.

  The clear hard coat layer forming coating solution used for forming the clear hard coat layer may contain a solvent, or may be appropriately contained and diluted as necessary. Examples of the organic solvent contained in the clear hard coat layer forming coating solution include hydrocarbons (eg, toluene, xylene, etc.), alcohols (eg, methanol, ethanol, isopropanol, butanol, cyclohexanol, etc.), ketones. (For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), esters (for example, methyl acetate, ethyl acetate, methyl lactate, etc.), glycol ethers, other organic solvents, or a mixture thereof. Available. Propylene glycol monoalkyl ether (1 to 4 carbon atoms of the alkyl group) or propylene glycol monoalkyl ether acetate ester (1 to 4 carbon atoms of the alkyl group) is 5% by mass or more, more preferably 5 to 80%. It is preferable to use the organic solvent containing at least mass%.

  Further, the clear hard coat layer can contain a silicone surfactant or a polyoxyether compound. The clear hard coat layer may contain a fluorine-siloxane graft polymer.

  These clear hard coat layers can be coated by a known wet coating method such as a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, and an inkjet method using a clear hard coat layer forming coating solution. it can.

  The coating amount of the hard coat layer coating solution is suitably from 0.1 to 40 μm, preferably from 0.5 to 30 μm, as the wet film thickness. The layer thickness is 0.1 to 30 μm, preferably 1 to 10 μm.

(Clear hard coat layer curing method)
After forming a clear hard coat layer on a film substrate whose surface has been subjected to vacuum ultraviolet irradiation treatment, the clear hard coat layer is irradiated with active energy rays, preferably ultraviolet rays, to finally form a clear hard coat layer. Harden.

As a light source used for curing the ultraviolet curable resin by a photocuring reaction and forming a cured clear hard coat layer, any light source that generates ultraviolet light can be used without any limitation. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. Irradiation conditions vary depending on each lamp, but the irradiation amount of active energy rays is preferably in the range of 5 to 100 mJ / cm ² , particularly preferably in the range of ^{20 to} 80 mJ / cm ² .

[Gas barrier layer]
As shown in FIG. 1, the gas barrier film of the present invention is characterized in that the gas barrier layer 5 is provided on the clear hard coat layer 4 formed as described above.

The gas barrier layer 5 according to the present invention has a water vapor permeability (25 ± 0.5 ° C., relative humidity 90 ± 2% RH) measured by a method according to JIS-K-7129-1992 of 0.01 g / (M ² · 24 hours) or less is preferable. Moreover, the oxygen permeability measured by the method based on JIS-K-7126-1987 is 1 × 10 ⁻³ ml / (m ² · 24 hours · atm) or less, and the water vapor permeability is 1 × 10 ⁻⁵ g / (M ² · 24 hours) or less is preferable.

  As a material for forming the gas barrier layer 5, a material having a function of suppressing intrusion of elements such as moisture and oxygen that cause performance deterioration of the organic EL element including the film substrate 2 and the gas barrier film 1, for example, Silicon oxide, silicon oxynitride, silicon dioxide, silicon nitride, or the like can be used.

  The formation method of the gas barrier layer 5 is not particularly limited. For example, the vacuum deposition method, the sputtering method, the reactive sputtering method, the molecular beam epitaxy method, the cluster ion beam method, the ion plating method, the plasma polymerization method, the atmospheric pressure plasma A formation method using a dry process such as a polymerization method, a plasma CVD method, a laser CVD method, or a thermal CVD method, or a formation method using a wet coating method can be used.

  As a method for forming the gas barrier layer 5 by a wet coating method, a coating liquid containing a polysilazane compound such as perhydroxypolysilazane is applied on a film substrate using a wet coating method, and then vacuum ultraviolet (excimer light) is used. Is applied to the inorganic film such as silicon oxide, silicon oxynitride, silicon nitride, etc. to form the gas barrier layer 5.

  For details of the method of forming the gas barrier layer of the wet coating method using excimer light as described above, for example, JP 2012-024933 A, JP 2012-121149 A, JP 2013-022799 A, Reference can be made to the descriptions of JP 2013-039786 A, JP 2013-025661 A, JP 2013-086445 A, and the like.

  In the present invention, from the viewpoint that a high-quality gas barrier layer can be stably formed, a method of forming a gas barrier layer by a chemical vapor deposition method (CVD method) is preferable, and a more precise gas is more preferable. From the viewpoint of forming a barrier layer, the chemical vapor deposition method is preferably a discharge plasma chemical vapor deposition method (plasma CVD method).

  Furthermore, from the viewpoint that the profile of the contained element distribution can be formed in an arbitrary pattern in the thickness direction of the gas barrier layer to be formed, as a discharge plasma chemical vapor deposition method (plasma CVD method), a resin substrate On one surface of the substrate, discharge plasma chemical vapor deposition having a discharge space between rollers to which a magnetic field having a structure as shown in FIG. 7 described later is applied using a source gas containing an organosilicon compound and oxygen gas A method of forming a gas barrier layer by a method is particularly preferable.

  Hereinafter, as an example of the gas barrier layer according to the present invention, a gas barrier layer forming method using a discharge plasma processing apparatus in which a discharge space is formed between rollers to which a magnetic field shown in FIG. 7 is applied will be described.

(1) Element profile of gas barrier layer Discharge plasma treatment having a discharge space between rollers to which a magnetic field as shown in FIG. 7 is applied in a gas barrier layer 5 constituting a gas barrier film 1 applied to an organic EL element. The gas barrier layer 5 formed by using the apparatus has a refractive index distribution in the layer thickness direction as its element profile, and is composed of an inorganic film having one or more extreme values in this refractive index distribution. Is preferred. The gas barrier layer 5 is made of a material containing silicon, oxygen, and carbon, and has a laminated structure including a plurality of layers having different contents of silicon, oxygen, and carbon.

  The gas barrier layer 5 has an arbitrary element profile in which the relationship between the distance from the surface of the gas barrier layer 5 in the layer thickness direction and the atomic weight ratio (atomic ratio) of each of the above elements (silicon, oxygen or carbon). Can be designed to

  In addition, the atomic ratio of silicon, oxygen, or carbon is represented by the ratio of silicon, oxygen, or carbon to the total amount of each element of silicon, oxygen, and carbon [(Si, O, C) / (Si + O + C)].

  The silicon distribution curve, the oxygen distribution curve, and the carbon distribution curve can be represented by an atomic ratio of silicon, an atomic ratio of oxygen, and an atomic ratio of carbon at a distance from the surface of the gas barrier layer 5. A distribution curve showing the relationship between the distance from the surface of the gas barrier layer 5 in the layer thickness direction and the ratio (atomic ratio) of the total atomic weight of oxygen and carbon is defined as an oxygen-carbon distribution curve.

The gas barrier layer 5 may further contain nitrogen in addition to silicon, oxygen and carbon. By containing nitrogen, the refractive index of the gas barrier layer 5 can be controlled. For example, the refractive index of SiO ₂ is 1.5, whereas the refractive index of SiN is about 1.8 to 2.0. For this reason, it becomes possible to set it as 1.6-1.8 which is a preferable refractive index value by containing nitrogen in the gas barrier layer 5 and forming SiON in the gas barrier layer 5. Thus, by applying the discharge plasma processing apparatus, the nitrogen content can be adjusted, and the refractive index of the gas barrier layer 5 can be controlled.

  When the gas barrier layer 5 contains nitrogen, the distribution curve of each element (silicon, oxygen, carbon or nitrogen) constituting the gas barrier layer 5 is as follows.

  In the case of containing nitrogen in addition to silicon, oxygen and carbon, the atomic ratio of silicon, oxygen, carbon or nitrogen is the ratio of silicon, oxygen, carbon or nitrogen to the total amount of each element of silicon, oxygen, carbon and nitrogen [(Si, O, C, N) / (Si + O + C + N)].

  The silicon distribution curve, oxygen distribution curve, carbon distribution curve, and nitrogen distribution curve represent the atomic ratio of silicon, the atomic ratio of oxygen, the atomic ratio of carbon, and the atomic ratio of nitrogen at a distance from the surface of the gas barrier layer 5, respectively. Show.

(2) Relationship between Element Distribution Curve and Refractive Index Distribution The refractive index distribution of the gas barrier layer 5 can be controlled by the amount of carbon and the amount of oxygen in the thickness direction of the gas barrier layer 5.

  FIG. 4 shows an example of the silicon distribution curve, oxygen distribution curve, carbon distribution curve, and nitrogen distribution curve of the gas barrier layer 5. 5 is an enlarged graph showing the carbon distribution curve from the silicon distribution curve, oxygen distribution curve, carbon distribution curve, and nitrogen distribution curve shown in FIG. 4 and 5, the horizontal axis indicates the distance (nm) from the surface of the gas barrier layer 5 in the layer thickness direction. The vertical axis indicates the atomic ratio (at%) of silicon, oxygen, carbon, or nitrogen with respect to the total amount of each element of silicon, oxygen, and carbon.

  In addition, the detail of the measuring method of a silicon distribution curve, an oxygen distribution curve, a carbon distribution curve, and a nitrogen distribution curve is mentioned later.

  As shown in FIG. 4, the atomic ratio of silicon, oxygen, carbon, and nitrogen changes depending on the distance from the surface of the gas barrier layer 5. In particular, with respect to oxygen and carbon, the atomic ratio varies greatly according to the distance from the surface of the gas barrier layer 5, and each distribution curve has a plurality of extreme values. In addition, the oxygen distribution curve and the carbon distribution curve are correlated, and the oxygen atomic ratio decreases at a distance where the carbon atomic ratio is large, and the oxygen atomic ratio increases at a distance where the carbon atomic ratio is small.

  FIG. 6 shows a refractive index distribution curve of the gas barrier layer 5. In FIG. 6, the horizontal axis indicates the distance [nm] from the surface of the gas barrier layer 5 in the layer thickness direction. The vertical axis represents the refractive index of the gas barrier layer 5. The refractive index of the gas barrier layer 5 shown in FIG. 6 is a measured value of the distance from the surface of the gas barrier layer 5 in the layer thickness direction and the refractive index of the gas barrier layer 5 with respect to visible light at this distance. The refractive index distribution of the gas barrier layer 5 can be measured using a known method, for example, a spectroscopic ellipsometer (ELC-300 manufactured by JASCO Corporation) or the like.

  As shown in FIGS. 5 and 6, there is a correlation between the atomic ratio of carbon and the refractive index of the gas barrier layer 5. Specifically, in the gas barrier layer 5, the refractive index of the gas barrier layer 5 also increases at the position where the carbon atomic ratio increases. Thus, the refractive index of the gas barrier layer 5 changes according to the atomic ratio of carbon. That is, in the gas barrier layer 5, the refractive index distribution curve of the gas barrier layer 5 can be controlled by adjusting the distribution of the atomic ratio of carbon in the layer thickness direction.

  Since the carbon atomic ratio and the oxygen atomic ratio are also correlated as described above, the refractive index distribution curve of the gas barrier layer 5 is controlled by controlling the oxygen atomic ratio and the distribution curve. be able to.

(3) Carbon distribution curve The gas barrier layer 5 requires that the carbon distribution curve has at least one extreme value. In such a gas barrier layer 5, it is more preferable that the carbon distribution curve has at least two extreme values, and it is even more preferable that the carbon distribution curve has at least three extreme values. Furthermore, it is preferable that the carbon distribution curve has at least one maximum value and one minimum value.

(4) Extreme Value In the gas barrier layer 5, the extreme value of the distribution curve is the maximum value or the minimum value of the atomic ratio of the element to the distance from the surface of the gas barrier layer 5 in the layer thickness direction of the gas barrier layer 5. Or it is the measured value of the refractive index distribution curve corresponding to the value.

  In the gas barrier layer 5, the maximum value of the distribution curve of each element is a point where the value of the atomic ratio of the element changes from increasing to decreasing when the distance from the surface of the gas barrier layer 5 is changed. In addition, from this point, the atomic ratio value of the element at a position where the distance from the surface of the gas barrier layer 5 is further changed by 20 nm is reduced by 3 at% or more.

  In the gas barrier layer 5, the minimum value of the distribution curve of each element is a point where the value of the atomic ratio of the element changes from decrease to increase when the distance from the surface of the gas barrier layer 5 is changed. In addition, from this point, the atomic ratio value of the element at a position where the distance from the surface of the gas barrier layer 5 is further changed by 20 nm is increased by 3 at% or more.

  In the carbon distribution curve of the gas barrier layer 5, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon is preferably 5 at% or more. In such a gas barrier layer 5, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon is more preferably 6 at% or more, and further preferably 7 at% or more. When the difference between the maximum value and the minimum value of the atomic ratio of carbon is less than the above range, the refractive index difference in the refractive index distribution curve of the obtained gas barrier layer 5 becomes small and the light distribution becomes insufficient.

  There is a correlation between the amount of carbon distribution and the refractive index, and when the absolute value of the maximum value and the minimum value of the preferable carbon atom is 7 at% or more, the absolute value of the difference between the maximum value and the minimum value of the obtained refractive index is It becomes 0.2 or more.

(5) Oxygen distribution curve The gas barrier layer 5 preferably has an oxygen distribution curve having at least one extreme value. In particular, the gas barrier layer 5 preferably has an oxygen distribution curve having at least two extreme values, and more preferably has at least three extreme values. Furthermore, it is preferable that the oxygen distribution curve has at least one maximum value and one minimum value.

  In the oxygen distribution curve of the gas barrier layer 5, the absolute value of the difference between the maximum value and the minimum value of the oxygen atomic ratio is preferably 5 at% or more. In such a gas barrier layer 5, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of oxygen is more preferably 6 at% or more, and further preferably 7 at% or more.

(6) Silicon distribution curve In the silicon distribution curve, the gas barrier layer 5 preferably has an absolute value of the difference between the maximum value and the minimum value of the atomic ratio of silicon of less than 5 at%. Further, in such a gas barrier layer 5, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of silicon is more preferably less than 4 at%, and further preferably less than 3 at%.

(7) Total amount of oxygen and carbon: oxygen carbon distribution curve In the gas barrier layer 5, the ratio of the total amount of oxygen atoms and carbon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms is expressed as oxygen. The carbon distribution curve.

  In the oxygen-carbon distribution curve, the gas barrier layer 5 preferably has an absolute value of the difference between the maximum value and the minimum value of the total atomic ratio of oxygen and carbon of less than 5 at%, more preferably less than 4 at%. Preferably, it is particularly preferably less than 3 at%.

(8) XPS depth profile The silicon distribution curve, oxygen distribution curve, carbon distribution curve, oxygen carbon distribution curve, and nitrogen distribution curve described above are measured by X-ray photoelectron spectroscopy (XPS), argon, and the like. By using together with the rare gas ion sputtering, it is possible to prepare by so-called XPS depth profile measurement in which the surface composition analysis is sequentially performed while exposing the inside of the sample. A distribution curve obtained by XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio (unit: at%) of each element and the horizontal axis as the etching time (sputtering time).

  In the element distribution curve having the horizontal axis as the etching time, the etching time generally correlates with the distance from the surface of the gas barrier layer 5 in the layer thickness direction. For this reason, when measuring the XPS depth profile, the distance from the surface of the gas barrier layer 5 calculated from the relationship between the etching rate and the etching time is defined as “the distance from the surface of the gas barrier layer 5 in the layer thickness direction”. Can be adopted.

For XPS depth profile measurement, a rare gas ion sputtering method using argon (Ar ⁺ ) as an etching ion species is employed, and an etching rate (etching rate) is set to 0.05 nm / sec (SiO ₂ thermal oxide film equivalent value). It is preferable to do.

  Moreover, it is preferable that the gas barrier layer 5 is substantially uniform in the surface direction (direction parallel to the surface of the gas barrier layer 5). The fact that the gas barrier layer 5 is substantially uniform in the plane direction means that the number of extreme values of the element distribution curves at the respective measurement locations is the same at any two locations on the surface of the gas barrier layer 5; And the absolute value of the difference between the maximum value and the minimum value of the carbon atomic ratio in the distribution curve is the same as each other, or the difference between the maximum value and the minimum value is within 5 at%.

(9) Layer thickness of gas barrier layer The layer thickness of the gas barrier layer 5 is preferably in the range of 5 to 3000 nm, more preferably in the range of 10 to 2000 nm, and in the range of 100 to 1000 nm. Particularly preferred.

  When the gas barrier layer 5 is formed from a plurality of layers, the total thickness of the gas barrier layer 5 is set in the range of 10 to 10,000 nm, preferably in the range of 10 to 5000 nm. More preferably, it is in the range of -3000 nm, and particularly preferably in the range of 200-2000 nm.

(10) Gas Barrier Layer Formation Method: Plasma Chemical Vapor Deposition In the present invention, the gas barrier layer 5 is preferably a layer formed by a plasma chemical vapor deposition (plasma CVD) method. As the gas barrier layer 5 formed by the plasma chemical vapor deposition method, for example, a discharge plasma processing apparatus as shown in FIG. 7 is used, and the film substrate 2 having the clear hard coat layer 4 formed on one surface is used. More preferably, it is a layer formed by a plasma chemical vapor deposition method that is disposed on a pair of film forming rollers and discharges between the pair of film forming rollers to generate plasma. The plasma enhanced chemical vapor deposition method may be a Penning discharge plasma type chemical vapor deposition method. Moreover, when discharging between a pair of film-forming rollers, it is preferable to reverse the polarity of a pair of film-forming rollers alternately.

  In the plasma chemical vapor deposition method, when generating plasma, it is preferable to generate plasma discharge in the space between the plurality of film forming rollers.

  Moreover, it is preferable to use the plasma chemical vapor deposition method by a counter roller system as a formation method of a gas barrier layer. In the present invention, the plasma chemical vapor deposition method using the opposed roller method uses a pair of film forming rollers, and a film substrate 2 on which a clear hard coat layer 4 is formed is disposed on each of the pair of film forming rollers. Thus, the gas barrier layer 5 is formed by generating a plasma by discharging between a pair of film forming rollers.

  Thus, by disposing the film base 2 having the clear hard coat layer 4 on a pair of film forming rollers and discharging between the film forming rollers, the film base existing on one film forming roller is disposed. A film can be formed on the material 2. At the same time, it is possible to form a film on the film substrate 2 on the other film forming roller. For this reason, the film-forming rate can be doubled and a thin film can be manufactured efficiently. Furthermore, the film | membrane of the same structure can be formed on each film base material 2 on a pair of film-forming roller.

  In the plasma chemical vapor deposition method, a film forming gas containing an organosilicon compound and oxygen is preferably used. The oxygen content in the film forming gas is preferably less than or equal to the theoretical oxygen amount necessary for complete oxidation of the entire amount of the organosilicon compound in the film forming gas.

  The gas barrier layer 5 is preferably a layer formed by a continuous film forming process.

(11) Apparatus for producing gas barrier layer 5 The gas barrier layer 5 may be formed on the film substrate 2 having the clear hard coat layer 4 in a roll-to-roll manner from the viewpoint of productivity as described above. preferable. An apparatus capable of producing the gas barrier layer 5 by the plasma chemical vapor deposition method is not particularly limited, but includes at least a pair of film forming rollers and a plasma power source, and discharges between the film forming rollers. It is preferable that the apparatus has a configuration capable of.

  For example, when a discharge plasma processing apparatus capable of forming a discharge space between rollers to which a magnetic field is applied as shown in FIG. 7 is used, it is continuously manufactured by a roll-to-roll method using a plasma chemical vapor deposition method. It is preferable from the viewpoint that it can be performed.

  Hereinafter, the manufacturing method of the gas barrier layer 5 is demonstrated, referring FIG.

  FIG. 7 is a schematic view showing an example of a discharge plasma processing apparatus suitable for forming a gas barrier layer according to the present invention.

  The discharge plasma processing apparatus 30 shown in FIG. 7 is a discharge plasma processing apparatus that can form a discharge space between rollers to which a magnetic field is applied. The discharge plasma processing apparatus 30 includes a feed roller 11, transport rollers 21, 22, 23, 24, Film rollers 31 and 32, a gas supply pipe 41, a plasma generation power source 51, magnetic field generators 61 and 62 installed inside the film formation rollers 31 and 32, and a winding roller 71 are provided. In the discharge plasma processing apparatus 30, at least film forming rollers 31 and 32, a gas supply pipe 41, a plasma generation power source 51, and magnetic field generation apparatuses 61 and 62 are disposed in a vacuum chamber (not shown). . Further, in the discharge plasma processing apparatus 30, the vacuum chamber is connected to a vacuum pump (not shown), and the pressure in the vacuum chamber can be adjusted by the vacuum pump.

  In the discharge plasma processing apparatus 30, each film formation roller has a plasma generation power source so that the pair of film formation rollers (the film formation roller 31 and the film formation roller 32) can function as a pair of counter electrodes. 51 is connected.

  For this reason, in the discharge plasma processing apparatus 30, it is possible to discharge to the space between the film forming roller 31 and the film forming roller 32 by supplying power from the plasma generating power supply 51. Plasma can be generated in the space between 31 and the film forming roller 32. In addition, when using the film-forming roller 31 and the film-forming roller 32 as an electrode, what is necessary is just to change the material and design of the film-forming roller 31 and the film-forming roller 32 so that it can also be used as an electrode.

  In the discharge plasma processing apparatus 30, the pair of film forming rollers (film forming rollers 31 and 32) is preferably arranged so that the central axes are substantially parallel on the same plane. Thus, by arranging a pair of film forming rollers (film forming rollers 31 and 32), the film forming rate can be doubled and a film having the same structure can be formed. For this reason, it is possible to at least double the extreme value in the carbon distribution curve. According to the discharge plasma processing apparatus 30, the gas barrier layer 5 can be formed on the clear hard coat layer 4 of the film base 2 by the CVD method. Since the film component can be deposited on the clear hard coat layer 4 of the film substrate 2 on the film forming roller 32 while the film component is deposited on the clear hard coat layer 4 of The gas barrier layer 5 can be efficiently formed on the clear hard coat layer 4 of 2.

  Further, inside the film forming roller 31 and the film forming roller 32, magnetic field generators 61 and 62 fixed so as not to rotate even when the film forming roller rotates are provided, respectively.

  Furthermore, as the film forming roller 31 and the film forming roller 32, known rollers can be used. As the film forming rollers 31 and 32, it is preferable to use rollers having the same diameter from the viewpoint of forming a thin film more efficiently. The diameters of the film forming rollers 31 and 32 are preferably in the range of 5 to 100 cm from the viewpoint of discharge conditions, chamber space, and the like.

  Further, in the discharge plasma processing apparatus 30, the film base is formed on a pair of film forming rollers (the film forming roller 31 and the film forming roller 32) so that the surfaces of the clear hard coat layer 4 of the film base 2 are opposed to each other. Material 2 is arranged. By disposing the film base 2 in this manner, when the plasma is generated by performing discharge between the film formation roller 31 and the film formation roller 32, the film base 2 existing between the pair of film formation rollers 2 It is possible to simultaneously form the gas barrier layer 5 on each surface of the clear hard coat layer 4 included. That is, according to the discharge plasma processing apparatus 30, a film component is deposited on the surface of the clear hard coat layer 4 of the film substrate 2 on the film forming roller 31 by the CVD method, and further on the film forming roller 32. Therefore, the gas barrier layer 5 can be efficiently formed on the surface of the clear hard coat layer 4 of the film substrate 2.

  Moreover, a well-known roller can be used as the sending-out roller 11 used for the discharge plasma processing apparatus 30, and the conveyance rollers 21, 22, 23, and 24. FIG. The winding roller 71 is not particularly limited as long as it can wind the film substrate 2 on which the gas barrier layer 5 is formed, and a known roller can be used.

  Further, as the gas supply pipe 41, a pipe capable of supplying or discharging the raw material gas at a predetermined speed can be used. Further, as the plasma generating power source 51, a power source of a known plasma generating apparatus can be used. The plasma generating power supply 51 supplies power to the film forming rollers 31 and 32 connected thereto, and enables the film forming rollers 31 and 32 to be used as counter electrodes for discharging. As the plasma generation power source 51, it is preferable to use an AC power source or the like capable of alternately reversing the polarity of the film forming roller because plasma CVD can be performed more efficiently. Moreover, since it becomes possible to perform plasma CVD more efficiently, the applied power can be 0.1 to 10 kW, and the alternating current frequency can be 0.05 to 500 kHz. It is more preferable to use the power source 51 for generation. As the magnetic field generators 61 and 62, known magnetic field generators can be used.

  As described above, using the discharge plasma processing apparatus 30 shown in FIG. 7, for example, the type of source gas, the power of the electrode drum of the plasma generator, the pressure in the vacuum chamber, the diameter of the film forming roller, and the film The gas barrier layer 5 can be manufactured by adjusting the conveyance speed. That is, the discharge plasma processing apparatus 30 shown in FIG. 7 is used to discharge between a pair of film forming rollers (film forming rollers 31 and 32) while supplying a film forming gas (raw material gas or the like) into the vacuum chamber. Thus, the film forming gas (raw material gas or the like) is decomposed by plasma, and the clear hard coating layer 4 on the surface of the film base 2 on the film forming roller 31 and the clear hard that the film base 2 on the film forming roller 32 has A gas barrier layer 5 is formed on the coat layer 4 by a plasma CVD method. In film formation, the film substrate 2 is conveyed by the delivery roller 11 and the film formation roller 31, respectively, so that the film substrate 2 is formed by a roll-to-roll continuous film formation process. A gas barrier layer 5 is formed on the clear hard coat layer 4.

(12) Source Gas The source gas contained in the film forming gas used for forming the gas barrier layer 5 can be appropriately selected and used according to the material of the gas barrier layer 5 to be formed. As the source gas, for example, an organosilicon compound containing silicon can be used.

  Examples of the organosilicon compound include hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propyl Examples thereof include silane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and octamethylcyclotetrasiloxane. Among these organosilicon compounds, hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane should be used from the viewpoints of handling in film formation and light distribution of the obtained gas barrier layer 5. Is preferred. Moreover, these organosilicon compounds can be used individually by 1 type or in combination of 2 or more types.

  In addition to the source gas, a reactive gas may be used as the film forming gas. As such a reactive gas, a gas that reacts with the raw material gas to become an inorganic compound such as an oxide or a nitride can be appropriately selected and used. As a reaction gas for forming an oxide, for example, oxygen gas or ozone gas can be used. Moreover, as a reactive gas for forming nitride, nitrogen gas and ammonia gas can be used, for example. These reaction gases can be used singly or in combination of two or more. For example, when forming an oxynitride, the reaction gas and nitride for forming an oxide are used. It can be used in combination with a reaction gas for forming.

  As the film forming gas, a carrier gas may be used as necessary in order to supply the source gas into the vacuum chamber. Further, as a film forming gas, a discharge gas may be used as necessary in order to generate plasma discharge. As the carrier gas and the discharge gas, a known gas can be used. For example, a rare gas such as helium, argon, neon, or xenon, or hydrogen gas can be used.

  When the film forming gas contains a source gas and a reactive gas, the ratio of the source gas and the reactive gas is the amount of the reactive gas that is theoretically necessary to completely react the raw material gas and the reactive gas. It is preferable not to make the ratio of the reaction gas excessively higher than the ratio of. If the ratio of the reaction gas is excessive, the light distribution of the gas barrier layer 5 cannot be obtained sufficiently. Moreover, when the film-forming gas contains an organosilicon compound and oxygen, the amount is preferably less than the theoretical oxygen amount necessary for complete oxidation of the entire amount of the organosilicon compound in the film-forming gas.

Hereinafter, as an example, a case where hexamethyldisiloxane (organosilicon compound: HMDSO: (CH ₃ ) ₆ Si ₂ O) is used as a source gas and oxygen (O ₂ ) is used as a reaction gas will be described.

  When a silicon-oxygen-based thin film is produced by reacting a film forming gas containing hexamethyldisiloxane as a source gas and oxygen as a reaction gas by plasma CVD, the reaction shown in the following reaction formula occurs by the film forming gas. Silicon dioxide is produced.

(CH ₃ ) ₆ Si ₂ O + 12O ₂ → 6CO ₂ + 9H ₂ O + 2SiO ₂
In the above reaction, the amount of oxygen required to completely oxidize 1 mol of hexamethyldisiloxane is 12 mol. For this reason, when 12 mol or more of oxygen is contained in 1 mol of hexamethyldisiloxane in the film forming gas and completely reacted, a uniform silicon dioxide film is formed. For this reason, the incomplete reaction is performed by controlling the gas flow rate ratio of the raw material to a flow rate equal to or lower than the theoretical reaction raw material ratio. That is, the amount of oxygen needs to be less than 12 moles of the stoichiometric ratio with respect to 1 mole of hexamethyldisiloxane.

  In the actual reaction in the plasma CVD chamber, since the raw material hexamethyldisiloxane and the reactive gas oxygen are supplied from the gas supply unit to the film formation region, the molar amount (flow rate) of the reactive gas oxygen is the raw material. Even if the molar amount (flow rate) is 12 times the molar amount (flow rate) of hexamethyldisiloxane, the reaction cannot actually proceed completely. That is, it is considered that the reaction is completed only when the oxygen content is supplied in a large excess compared to the stoichiometric ratio. For example, in order to obtain silicon oxide by complete oxidation by CVD, the molar amount (flow rate) of oxygen may be about 20 times or more the molar amount (flow rate) of hexamethyldisiloxane as a raw material.

  For this reason, it is preferable that the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of the raw material hexamethyldisiloxane is 12 times or less (more preferably 10 times or less) which is the stoichiometric ratio. By containing hexamethyldisiloxane and oxygen in such a ratio, carbon atoms and hydrogen atoms in hexamethyldisiloxane that have not been completely oxidized are taken into the gas barrier layer 5, and the desired gas barrier layer 5. Can be formed.

  If the molar amount (flow rate) of oxygen relative to the molar amount (flow rate) of hexamethyldisiloxane in the film forming gas is too small, unoxidized carbon atoms and hydrogen atoms are excessively taken into the gas barrier layer 5. Therefore, the transparency of the gas barrier layer 5 is lowered. For this reason, like the organic EL element 10, it cannot be used for a flexible substrate that requires transparency. From such a viewpoint, the lower limit of the molar amount (flow rate) of oxygen relative to the molar amount (flow rate) of hexamethyldisiloxane in the film forming gas is more than 0.1 times the molar amount (flow rate) of hexamethyldisiloxane. Preferably, the amount is more than 0.5 times.

(13) Degree of vacuum The pressure (degree of vacuum) in the vacuum chamber can be appropriately adjusted according to the type of the raw material gas, but is preferably in the range of 0.5 to 100 Pa.

(14) Film Formation Roller In the plasma CVD method described above, the electric power applied to the electrode drum connected to the plasma generating power source 51 for discharging between the film formation rollers 31 and 32 depends on the type of material gas and the vacuum. It can be appropriately adjusted according to the pressure in the chamber. For example, a range of 0.1 to 10 kW is preferable. If the applied power is 0.1 kW or more, the generation of particles can be suppressed. On the other hand, if the applied power is 10 kW or less, the amount of heat generated at the time of film formation can be suppressed, an increase in the temperature of the base material surface at the time of film formation can be prevented, and the film base material 2 generates wrinkles due to excessive heat. Can be prevented.

  The electrode drum is usually installed on the film forming rollers 31 and 32.

  Although the conveyance speed (line speed) of the film base material 2 can be suitably adjusted according to the kind of source gas, the pressure in a vacuum chamber, etc., it is preferable to set it as the range of 0.25-100 m / min. More preferably, it is in the range of 0.5 to 20 m / min. If the line speed is 0.25 m / min or more, generation of wrinkles due to heat can be prevented in the film substrate 2, while if it is 100 m / min or less, the thickness of the gas barrier layer 5 to be formed is desired. It becomes easy to be within the range.

  The gas barrier layer 5 is formed from an inorganic film containing silicon, oxygen, and carbon, and has a characteristic of excellent thermal diffusivity. In particular, the inclusion of carbon is considered to improve the thermal conductivity as compared with an inorganic film made only of silicon and oxygen. Since the gas barrier layer 5 has a carbon content distribution in the layer thickness direction, it is presumed that the gas barrier layer 5 has characteristics similar to a configuration in which a plurality of layers having different compositions are laminated. That is, excellent thermal diffusibility is obtained in a region having a high carbon content in the gas barrier layer 5, and thermal diffusivity in the surface direction of the gas barrier layer 5 is improved. For this reason, the thermal diffusibility of the gas barrier layer 5 can be improved.

  Therefore, when the thermosetting resin is used for the sealing resin layer 19 and the high temperature treatment is performed for a long time as the curing treatment, the heat applied to the organic EL element 10 is dissipated by the gas barrier layer 5, thereby Thermal damage to the material 12 can be reduced.

[Other component layers]
In addition to the constituent layers described above, other functional layers may be provided in the gas barrier film of the present invention as long as the object and effects of the present invention are not impaired.

  For example, on a gas barrier layer 5 formed by a bleed-out prevention layer, a smooth layer, or the above-described discharge plasma chemical vapor deposition method (plasma CVD method), a wet coating method is further used to combine polysilazane and excimer light treatment. It is also possible to provide a polysilazane modified layer.

[Heat resistant laminate]
In the gas barrier film of the present invention, as shown in FIG. 1, the surface side (back surface side) opposite to the surface (front surface) provided with the clear hard coat layer 4 and the gas barrier layer 5 of the film base 2. Further, the heat-resistant laminate member 6 is provided.

  By providing the heat-resistant laminate member 6 on the back side of the film base 2, excessive thermal energy is given to the film base 2 in particular in the manufacturing process of the gas barrier film as illustrated in FIG. 2. When performing the vacuum ultraviolet ray treatment in the process, for example, the process A shown in 3) of FIG. 2, in the process B shown in 4) of FIG. 2, the heating and drying process after applying the clear hard coat layer 4A, FIG. 5) When the clear hard coat layer 4A is formed by curing the clear hard coat layer 4A in the process C, a thermosetting treatment using a thermosetting resin or an ultraviolet irradiation process using an ultraviolet curable resin is used. Alternatively, in the process D shown in 6) of FIG. 2, the film substrate receives damage to the thermal energy applied in each process, such as a plasma discharge treatment process when the gas barrier layer 5 is formed. Hesi invariably be a good film substrate flatness.

  Further, when the gas barrier layer 5 is formed using the discharge plasma processing apparatus shown in FIG. 7 described above, when the film base material 2 is transported, the back surface of the film base material 2 and the back contact type rollers. It is also possible to prevent scratches due to contact with the surface.

  In addition, when the gas barrier film of the present invention is finally provided in an organic EL element, the applied heat resistant laminate member 6 is used in a removed form.

  The heat-resistant laminate member according to the present invention is mainly composed of a heat-resistant film, an adhesive layer and a release sheet, and when used, the release sheet is peeled off and the adhesive layer is bonded to the back side of the film substrate according to the present invention. And use it.

  Although there is no restriction | limiting in particular as a heat resistant film which comprises the heat resistant laminate member applicable to the gas barrier film of this invention, The glass transition temperature of the cycloolefin polymer or cycloolefin copolymer which comprises a film base material is about 100-160. It is preferably formed of a film material having a melting point and a glass transition temperature (Tg) higher than about 0 ° C. Examples of the heat-resistant film that can be used in the heat-resistant laminate member include a polyethylene naphthalate film (for example, Q83 (trade name) manufactured by Teijin DuPont, Tg: 262 ° C.), a polyethylene terephthalate film (for example, manufactured by Toyobo, Toyobo polyester) (Registered trademark) film (trade name), melting point: 260 ° C., polyimide film (for example, Neoprim L-3430 (Tg: 303 ° C.), L-1000 (Tg: 260 ° C.), L-9000 (manufactured by Mitsubishi Gas Co., Ltd.) Tg: 315 ° C.), polyamide film (Unitika Ltd. Tg: 280 ° C.), and the like.

  In addition, the configuration of the pressure-sensitive adhesive layer applicable to the present invention is not particularly limited, and for example, any of a dry laminating agent, a wet laminating agent, a pressure-sensitive adhesive, a heat seal agent, a hot melt agent, and the like is used. As the adhesive, for example, a polyester resin, a urethane resin, a polyvinyl acetate resin, an acrylic resin, a nitrile rubber, or the like is used. In addition, a gel or sol of a polymer compound and an organic solvent or oil, an aqueous emulsion of the polymer compound, a sol or gel in which a polymer compound and a water-soluble polymer are dissolved and dispersed in a hydrophilic solvent, and the like can be given.

  Examples of the release sheet include an acrylic film or sheet, a polycarbonate film or sheet, a polyarylate film or sheet, a polyethylene naphthalate film or sheet, a polyethylene terephthalate film or sheet, a plastic film or sheet such as a fluorine film, or titanium oxide. Resin film or sheet kneaded with silica, aluminum powder, copper powder, etc., and resin film or sheet with surface treatment such as coating the resin kneaded with these or metal depositing metal such as aluminum A material is used.

  Moreover, in this invention, a commercial item can be used as it is as a heat-resistant laminate member. For example, heat-resistant protective film Masudak (registered trademark) PC (for example, product name normal type PC-542PA, adhesive low transition type PC-751, PC-801) manufactured by Fujimori Kogyo Co., Ltd. may be mentioned. This heat-resistant protective film has a structure in which an adhesive layer (4 to 10 μm) and a release film (thickness 40 μm) are laminated on a low heat-shrinkable polyester film having a thickness of 50 μm. Moreover, the surface protection film for optics Masudak (trademark) TFB (For example, product name ZBO-0421, NBO-0424, TFB-4T3-367AS) is similarly mentioned from Fujimori Kogyo Co., Ltd.

《Organic electroluminescence device》
[Schematic configuration of organic EL element]
Next, a specific configuration of the organic electroluminescence element of the present invention will be described.

  FIG. 8 is a schematic configuration diagram showing an example of the configuration of the organic EL element provided with the gas barrier film of the present invention.

  As shown in FIG. 8, the organic EL element 101 mainly includes a gas barrier film 1, a first electrode 116, an organic functional layer 117, a second electrode 118, a sealing resin layer 119, and a sealing member 120. It is composed of The gas barrier film 1 of the present invention is configured by laminating a clear hard coat layer 4 and a gas barrier layer 5 in this order on a film substrate 2.

  In the organic EL element 101 shown in FIG. 8, an organic functional layer 117 including a light emitting layer and a second electrode 118 serving as a cathode are laminated on a first electrode 116 serving as an anode, and further, the gas barrier film 1 and the sealing layer are sealed. The structure is solid-sealed by the stop resin layer 119 and the sealing member 120. Among these, the 1st electrode 116 used as an anode is comprised as a translucent electrode. In such a configuration, only a portion where the organic functional layer 117 is sandwiched between the first electrode 116 and the second electrode 118 becomes a light emitting region in the organic EL element 101. In the example shown in FIG. 8, the organic EL element 101 is configured as a bottom emission type in which generated light (hereinafter referred to as emitted light h) is extracted at least from the gas barrier film 1 side.

  In the organic EL element 101, a sealing member 120 is bonded on one surface of the gas barrier film 1 via a sealing resin layer 119 that covers the first electrode 116, the organic functional layer 117, and the second electrode 118. By doing so, it is solid-sealed. In the solid-sealed organic EL element 101, an uncured resin material is applied to the bonding surface of the sealing member 120, or the gas barrier layer 5 of the gas barrier film 1 and a plurality of locations of the second electrode 118, The gas barrier film 1 and the sealing member 120 are integrated by thermocompression bonding with the resin material interposed therebetween.

The organic EL element 101 is not limited to the bottom emission type. For example, the organic EL element 101 may have a top emission type configuration in which light is extracted from the second electrode 118 side or a dual emission type configuration in which light is extracted from both sides. If the organic EL element 101 is a top emission type, a transparent material is used for the second electrode 118 and the emitted light h is extracted from the second electrode 118 side. Further, when the organic EL element 101 is a double-sided light emitting type, a transparent material is used for the second electrode 118 and the emitted light h is extracted from both sides.

[Components of organic EL elements]
Hereinafter, detailed configurations of the first electrode 116, the second electrode 118, the organic functional layer 117, the sealing resin layer 119, and the sealing member 120, excluding the gas barrier film 1 already described, will be described. In addition, in the organic EL element 101 of this invention, translucency means that the light transmittance in wavelength 550nm is 50% or more.

(First electrode)
In the organic EL element 101 shown in FIG. 8, the first electrode 116 is a substantial anode. The organic EL element 101 is a bottom emission type element that passes through the first electrode 116 and extracts light from the film base 2 side. For this reason, the first electrode 116 needs to be formed of a light-transmitting conductive layer.

  The first electrode 116 is a layer formed using, for example, silver or an alloy containing silver as a main component. Examples of the alloy mainly composed of silver (Ag) constituting the first electrode 116 include silver magnesium (AgMg), silver copper (AgCu), silver palladium (AgPd), silver palladium copper (AgPdCu), and silver indium ( AgIn) and the like. In the first electrode, the main component means that the content in the electrode is 98% by mass or more.

  The first electrode 116 may be formed by laminating a plurality of layers of silver or an alloy containing silver as a main component.

  Examples of a method for forming the first electrode 116 include a method using a wet process such as a coating method, an inkjet method, a coating method, and a dip method, a vapor deposition method (resistance heating, EB method, etc.), a sputtering method, a CVD method, and the like. And a method using the dry process. Of these, the vapor deposition method is preferably applied.

  Further, the first electrode 116 preferably has a thickness in the range of 4 to 12 nm. A thickness of 12 nm or less is preferable because the light absorption component and the reflection component can be kept low and the light transmittance can be secured. Further, it is preferable that the thickness is 4 nm or more because sufficient conductivity as an electrode can be secured.

  Note that the upper portion of the first electrode 116 may be covered with a protective film, or another conductive layer may be laminated. In this case, it is preferable that the protective film and the conductive layer have light transmittance so that the light transmittance of the organic EL element 101 is not impaired.

  Moreover, it is good also as a structure which provided the layer according to the necessity under the 1st electrode 116, ie, between the gas barrier layer 5 and the 1st electrode 116. FIG. For example, the first electrode 116 may have an underlayer or the like for improving the characteristics or facilitating the formation.

  In addition, the first electrode 116 may have a configuration other than the main component of silver. For example, various transparent conductive material thin films such as other metals and alloys, ITO, zinc oxide, tin oxide and the like may be used.

  In addition, when the organic EL element 101 is a top emission type in which the emitted light h is extracted from the second electrode 118 side, the first electrode 116 may not have translucency.

(Second electrode)
The second electrode 118 is an electrode layer that functions as a cathode for supplying electrons to the organic functional layer 117, and a metal, an alloy, an organic or inorganic conductive compound, and a mixture thereof are used as a constituent material. Specifically, gold, aluminum, silver, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, indium, lithium / aluminum mixture, rare earth metal, ITO, ZnO, TiO ₂ and oxide semiconductors such as SnO ₂ .

  The second electrode 118 can be formed using such a conductive material by a method such as vapor deposition or sputtering. The sheet resistance as the second electrode 118 is several hundred Ω / sq. The following is preferable, and the thickness is usually selected in the range of 5 to 5000 nm, preferably 5 to 200 nm.

  In addition, when the organic EL element 101 is a top emission type or a double-sided emission type that takes out the emitted light h from the second electrode 118 side, a conductive material having good light transmittance is selected from the above-described conductive materials. Thus, the second electrode 118 is configured.

(Organic functional layer)
The organic functional layer 117 has a configuration in which a hole injection layer 117a / a hole transport layer 117b / a light emitting layer 117c / an electron transport layer 117d / an electron injection layer 117e are stacked in this order on the first electrode 116 serving as an anode. Although it is possible, it is necessary to have at least the light emitting layer 117c formed using an organic material. The hole injection layer 117a and the hole transport layer 117b may be provided as a single layer hole transport / injection layer having a hole transport property and a hole injection property. The electron transport layer 117d and the electron injection layer 117e may be provided as a single-layer electron transport / injection layer having an electron transport property and an electron injection property. Among these organic functional layers 117, for example, the electron injection layer 117e may be made of an inorganic material.

  In addition to these layers, for example, a hole blocking layer, an electron blocking layer, or the like may be stacked on the organic functional layer 117 at a necessary position as necessary. Further, the light emitting layer 117c has each color light emitting layer for generating light emission in each wavelength region, and each color light emitting layer is laminated through a non-light emitting intermediate layer to form a light emitting layer unit. Also good. The intermediate layer may function as a hole blocking layer and an electron blocking layer.

<Light emitting layer>
The light emitting layer 117c contains, for example, a phosphorescent light emitting compound as a light emitting material.

  The light emitting layer 117c is a layer that emits light by recombination of electrons injected from the electrode or the electron transport layer 117d and holes injected from the hole transport layer 117b, and the light emitting portion is the light emitting layer 117c. Even within the layer, it may be an interface between the light emitting layer 117c and the adjacent layer.

  There is no particular limitation on the structure of the light emitting layer 117c as long as the light emitting material included satisfies the light emission requirements. Moreover, there may be a plurality of layers having the same emission spectrum and emission maximum wavelength. In this case, it is preferable to have a non-light emitting intermediate layer (not shown) between the light emitting layers 117c.

  The total thickness of the light emitting layer 117c is preferably in the range of 1 to 100 nm, and more preferably in the range of 1 to 30 nm because it can be driven at a lower voltage. Note that the sum of the layer thicknesses of the light-emitting layer 117c is a layer thickness including the intermediate layer when a non-light-emitting intermediate layer exists between the light-emitting layers 117c.

  When the light emitting layer 117c is composed of a plurality of layers, the thickness of each light emitting layer is preferably adjusted within a range of 1 to 50 nm, and more preferably adjusted within a range of 1 to 20 nm. When the plurality of stacked light emitting layers correspond to the respective emission colors of blue, green, and red, there is no particular limitation on the relationship between the thicknesses of the blue, green, and red light emitting layers.

  The light emitting layer 117c as described above can be formed of a light emitting material or a host compound, which will be described later, by a known thin film forming method such as a vacuum deposition method, a spin coating method, a casting method, an LB method, or an ink jet method.

  The light-emitting layer 117c may contain a plurality of light-emitting materials, or a phosphorescent light-emitting material and a fluorescent light-emitting material (also referred to as a fluorescent dopant or a fluorescent compound) may be mixed and used in the same light-emitting layer 117c. Good.

  The light-emitting layer 117c preferably includes a host compound (also referred to as a light-emitting host) and a light-emitting material (also referred to as a light-emitting dopant compound or a guest material) and emits light from the light-emitting material.

(1) Host Compound As the host compound contained in the light emitting layer 117c, a compound having a phosphorescence quantum yield of phosphorescence emission at room temperature (25 ° C.) of less than 0.1 is preferable. Furthermore, the compound whose phosphorescence quantum yield is less than 0.01 is preferable. In addition, the host compound preferably has a volume ratio in the layer of 50% or more among the compounds contained in the light emitting layer 117c.

  As a host compound, a well-known host compound may be used independently, or multiple types may be used. By using a plurality of types of host compounds, it is possible to adjust the movement of charges, and the organic EL element 101 can be made highly efficient. In addition, by using a plurality of kinds of light emitting materials described later, it is possible to mix different light emission, thereby obtaining an arbitrary light emission color.

  The host compound used may be a conventionally known low molecular compound, a high molecular compound having a repeating unit, or a low molecular compound having a polymerizable group such as a vinyl group or an epoxy group (evaporation polymerizable light emitting host). .

  As the known host compound, a compound that has a hole transporting ability and an electron transporting ability, prevents light emission from being increased in wavelength, and has a high Tg (glass transition temperature) is preferable. The glass transition point (Tg) here is a value obtained by a method based on JIS-K-7121 using DSC (Differential Scanning Colorimetry).

(2) Light-Emitting Material Examples of the light-emitting material that can be used for the organic EL element 101 include a phosphorescent compound (also referred to as a phosphorescent compound or a phosphorescent material) and a fluorescent compound.

  A phosphorescent compound is a compound in which light emission from an excited triplet is observed. Specifically, it is a compound that emits phosphorescence at room temperature (25 ° C.), and the phosphorescence quantum yield is 0 at 25 ° C. A preferred phosphorescence quantum yield is 0.1 or more, although it is defined as 0.01 or more compounds.

  The phosphorescence quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of Experimental Chemistry Course 4 of the 4th edition. Although the phosphorescence quantum yield in a solution can be measured using various solvents, in the case where a phosphorescent compound is used in this example, the phosphorescence quantum yield (0.01 or more) is obtained in any solvent. It only has to be achieved.

  There are two types of light emission principles of the phosphorescent compound. One is that recombination of carriers occurs on the host compound to which carriers are transported to generate an excited state of the host compound, and this energy is transferred to the phosphorescent compound to emit light from the phosphorescent compound. Energy transfer type. The other is a carrier trap type in which the phosphorescent compound becomes a carrier trap, and recombination of carriers occurs on the phosphorescent compound, and light emission from the phosphorescent compound is obtained. In either case, the condition is that the excited state energy of the phosphorescent compound is lower than the excited state energy of the host compound.

  The phosphorescent compound can be appropriately selected from known compounds used for the light emitting layer of a general organic EL device, but preferably contains a group 8-10 metal in the periodic table of elements. It is a complex compound. More preferred are iridium compounds, osmium compounds, platinum compounds (platinum complex compounds), and rare earth complexes, and most preferred are iridium compounds.

  In the organic EL element 101, at least one light emitting layer 117c may contain two or more phosphorescent compounds, and the concentration ratio of the phosphorescent compound in the light emitting layer 117c is the layer thickness of the light emitting layer 117c. It may change in direction.

  The phosphorescent compound is preferably 0.1% by volume or more and less than 30% by volume with respect to the total amount of the light emitting layer 117c.

  Examples of the fluorescent light emitting material used for the light emitting layer 117c include, for example, a coumarin dye, a pyran dye, a cyanine dye, a croconium dye, a squalium dye, an oxobenzanthracene dye, a fluorescein dye, a rhodamine dye, Examples include pyrylium dyes, perylene dyes, stilbene dyes, polythiophene dyes, and rare earth complex phosphors.

<Injection layer>
The injection layer is a layer provided between the electrode and the light emitting layer 117c in order to lower the driving voltage and improve the light emission luminance. “The organic EL element and the forefront of its industrialization (November 30, 1998, NT. 2) Chapter 2 “Electrode Materials” (pages 123 to 166) of the 2nd volume of “S Corp.”, and includes a hole injection layer 117a and an electron injection layer 117e.

  The injection layer can be provided as necessary. The hole injection layer 117a is disposed between the anode and the light emitting layer 117c or the hole transport layer 117b, and the electron injection layer 117e is disposed between the cathode and the light emitting layer 117c or the electron transport layer 117d.

  The details of the hole injection layer 117a are described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069, and the like. Specific examples thereof include phthalocyanine represented by copper phthalocyanine. Examples thereof include a layer, an oxide layer typified by vanadium oxide, an amorphous carbon layer, and a polymer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene.

  The details of the electron injection layer 117e are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like, and specifically, strontium, aluminum and the like are represented. Examples thereof include a metal layer, an alkali metal halide layer typified by potassium fluoride, an alkaline earth metal compound layer typified by magnesium fluoride, and an oxide layer typified by molybdenum oxide. The electron injection layer 17e is desirably a very thin layer, and its thickness is preferably in the range of 0.001 to 10 μm although it depends on the material.

<Hole transport layer>
The hole transport layer 117b is made of a hole transport material having a function of transporting holes. In a broad sense, the hole injection layer 117a and the electron blocking layer are also included in the hole transport layer 117b. The hole transport layer 117b can be provided as a single layer or a plurality of layers.

  The hole transport material has any of hole injection or transport and electron barrier properties, and may be either organic or inorganic. For example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, Examples thereof include stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers.

  Although the above-mentioned thing can be used as a positive hole transport material, It is preferable to use a porphyrin compound, an aromatic tertiary amine compound, and a styryl amine compound, especially an aromatic tertiary amine compound.

  Representative examples of aromatic tertiary amine compounds and styrylamine compounds include N, N, N ', N'-tetraphenyl-4,4'-diaminophenyl; N, N'-diphenyl-N, N'- Bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine (abbreviation: TPD); 2,2-bis (4-di-p-tolylaminophenyl) propane; -Bis (4-di-p-tolylaminophenyl) cyclohexane; N, N, N ', N'-tetra-p-tolyl-4,4'-diaminobiphenyl; 1,1-bis (4-di-p -Tolylaminophenyl) -4-phenylcyclohexane; bis (4-dimethylamino-2-methylphenyl) phenylmethane; bis (4-di-p-tolylaminophenyl) phenylmethane; N, N'-diphenyl-N, '-Di (4-methoxyphenyl) -4,4'-diaminobiphenyl; N, N, N', N'-tetraphenyl-4,4'-diaminodiphenyl ether; 4,4'-bis (diphenylamino) c N, N, N-tri (p-tolyl) amine; 4- (di-p-tolylamino) -4 '-[4- (di-p-tolylamino) styryl] stilbene; 4-N, N- Diphenylamino- (2-diphenylvinyl) benzene; 3-methoxy-4'-N, N-diphenylaminostilbenzene; N-phenylcarbazole and also two condensations described in US Pat. No. 5,061,569 Those having an aromatic ring in the molecule, for example, 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (abbreviation: NPD), 4,4 ′, 4 ″ -tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine in which triphenylamine units described in Japanese Patent No. 08688 are linked in three starburst forms ( (Abbreviation: MTDATA).

  Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used. In addition, inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole injection material and the hole transport material.

  In addition, in the hole transport layer 117b, JP-A-11-251067, J. Org. Huang et. al. , Applied Physics Letters, 80 (2002), p. A so-called p-type hole transport material as described in 139 can also be used. These materials are preferably used because a highly efficient light-emitting element can be obtained.

  The hole transport layer 117b is formed by thinning the hole transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an inkjet method, or an LB method. be able to.

  Although there is no restriction | limiting in particular about the layer thickness of the positive hole transport layer 117b, Usually, about 5-5000 nm, Preferably it exists in the range of 5-200 nm. The hole transport layer 117b may have a single layer structure composed of one or more of the above materials.

  Alternatively, the material of the hole transport layer 117b can be doped with impurities to increase the p property. Examples thereof include JP-A-4-297076, JP-A-2000-196140, 2001-102175, J.A. Appl. Phys. 95, 5773 (2004), and the like.

  Thus, it is preferable to increase the p property of the hole transport layer 117b because an element with lower power consumption can be manufactured.

<Electron transport layer>
The electron transport layer 117d is made of a material having a function of transporting electrons. In a broad sense, the electron injection layer 117e and a hole blocking layer (not shown) are also included in the electron transport layer 117d. The electron transport layer 117d can be provided as a single layer structure or a stacked structure of a plurality of layers.

  As an electron transport material (also serving as a hole blocking material) constituting a layer portion adjacent to the light emitting layer 117c in the electron transport layer 117d having a single layer structure and the electron transport layer 117d having a multilayer structure, electrons injected from the cathode are used. What is necessary is just to have the function to transmit to the light emitting layer 117c. Such a material can be arbitrarily selected from conventionally known compounds. Examples include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane, anthrone derivatives, and oxadiazole derivatives. Further, in the above oxadiazole derivative, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron-withdrawing group are also used as the material for the electron transport layer 117d. Can do. Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.

In addition, metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (abbreviation: Alq ₃ ), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8- Quinolinol) aluminum, tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (abbreviation: Znq), etc., and the central metal of these metal complexes A metal complex in which In, Mg, Cu, Ca, Sn, Ga, or Pb is replaced can also be used as the material of the electron transport layer 117d.

  In addition, even when metal-free or metal phthalocyanine or the terminal thereof is substituted with an alkyl group or a sulfonic acid group, it can be preferably used as the material for the electron transport layer 117d. Further, a distyrylpyrazine derivative exemplified also as a material of the light-emitting layer 117c can be used as a material of the electron-transport layer 117d, and similarly to the hole-injection layer 117a and the hole-transport layer 117b, n-type -Si, n An inorganic semiconductor such as type-SiC can also be used as the material of the electron transport layer 117d.

  The electron transport layer 117d can be formed by thinning the above material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an inkjet method, or an LB method. Although there is no restriction | limiting in particular about the layer thickness of the electron carrying layer 117d, Usually, it is about 5-5000 nm, Preferably it exists in the range of 5-200 nm. The electron transport layer 117d may have a single-layer structure made of one or more of the above materials.

  In addition, the electron transport layer 117d can be doped with an impurity to increase n property. Examples thereof include JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140, 2001-102175, J.A. Appl. Phys. 95, 5773 (2004), and the like. Furthermore, it is preferable that the electron transport layer 117d contains potassium, a potassium compound, or the like. As the potassium compound, for example, potassium fluoride can be used. Thus, when the n property of the electron transport layer 117d is increased, a device with lower power consumption can be manufactured.

<Blocking layer>
As described above, the blocking layer is provided as necessary in addition to the basic constituent layer of the organic compound thin film. For example, it is described in JP-A Nos. 11-204258, 11-204359, and “Organic EL elements and their forefront of industrialization” (issued by NTT, Inc. on November 30, 1998). There is a hole blocking (hole blocking) layer.

  In a broad sense, the hole blocking layer has the function of the electron transport layer 117d. The hole blocking layer is made of a hole blocking material that has a function of transporting electrons but has a very small ability to transport holes, and recombines electrons and holes by blocking holes while transporting electrons. Probability can be improved. Moreover, the structure of the electron carrying layer 117d mentioned later can be used as a hole-blocking layer as needed. The hole blocking layer is preferably provided adjacent to the light emitting layer 117c.

  On the other hand, the electron blocking layer has a function of the hole transport layer 117b in a broad sense. The electron blocking layer is made of a material that has a function of transporting holes but has a very small ability to transport electrons, and improves the probability of recombination of electrons and holes by blocking electrons while transporting holes. be able to. The structure of the hole transport layer 117b described above can be used as an electron blocking layer as necessary.

  The thickness of the blocking layer is preferably 3 to 100 nm, more preferably 5 to 30 nm.

(Sealing member)
The sealing member 120 covers the organic EL element 101, and the plate-like (film-like) sealing member 120 is fixed to the film base 2 side of the gas barrier film by the sealing resin layer 119. . The sealing member 120 is provided so as to cover at least the organic functional layer 117, and is provided so as to expose the terminal portions (not shown) of the organic EL element 101 and the second electrode 118. Further, an electrode may be provided on the sealing member 120 and the electrode and the terminal portion of the second electrode 118 may be electrically connected.

  Specific examples of the plate-like (film-like) sealing member 120 include a glass substrate and a polymer substrate, and these substrate materials may be used in the form of a thinner film. Examples of the glass substrate include soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz. Examples of the polymer substrate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone.

  In particular, since the element can be thinned, a polymer substrate in the form of a thin film can be preferably used as the sealing member 120.

Furthermore, the polymer substrate in the form of a film has an oxygen permeability measured by a method according to JIS-K-7126-1987 of 1 × 10 ⁻³ ml / (m ² · 24 h · atm) or less, JIS-K. The water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) measured by a method based on −7129-1992 is 1 × 10 ⁻³ g / (m ² · 24 h) or less. It is preferable that

  Further, the substrate material as described above may be processed into a concave plate shape and used as the sealing member 120. In this case, the above-described substrate member is subjected to processing such as sand blasting or chemical etching to form a concave shape.

  Moreover, not only this but a metal material may be used. Examples of the metal material include one or more metals or alloys selected from the group consisting of stainless steel, iron, copper, aluminum, magnesium, nickel, zinc, chromium, titanium, molybdenum, silicone, germanium, and tantalum. By using such a metal material in the form of a thin film as the sealing member 120, the entire light emitting panel provided with the organic EL element 101 can be thinned.

<Sealing resin layer>
The sealing resin layer 119 for fixing the sealing member 120 to the gas barrier film 1 side is used for sealing the organic EL element 101 sandwiched between the sealing member 120 and the gas barrier film 1. The sealing resin layer 119 is, for example, a photocurable or thermosetting adhesive having a reactive vinyl group of an acrylic acid-based oligomer or a methacrylic acid-based oligomer, an epoxy-based thermosetting or chemical curable (two-component). Mixed) adhesives, hot-melt type polyamides, polyesters, polyolefins, and cationic curing type ultraviolet curable epoxy resins.

  From the viewpoint of simplicity of the manufacturing process, it is preferable to form the sealing resin layer 119 with a thermosetting adhesive. Moreover, as a form of the sealing resin layer 119, it is preferable to use a thermosetting adhesive processed into a sheet shape. When a sheet-like thermosetting adhesive is used, the adhesive exhibits non-fluidity at room temperature (about 25 ° C.) and exhibits fluidity at a temperature in the range of 50 to 130 ° C. when heated. (Sealant) is used.

  As the thermosetting adhesive, any adhesive can be used. From the viewpoint of improving the adhesion with the sealing member 120 adjacent to the sealing resin layer 119, the gas barrier film 1 and the like, a suitable thermosetting adhesive is appropriately selected. For example, as the thermosetting adhesive, it is possible to use a resin mainly composed of a compound having an ethylenic double bond at the terminal or side chain of a molecule and a thermal polymerization initiator. More specifically, a thermosetting adhesive made of an epoxy resin, an acrylic resin, or the like can be used. Moreover, according to the bonding apparatus and hardening processing apparatus which are used by the manufacturing process of the organic EL element 101, you may use a fusion type thermosetting adhesive.

  Moreover, what mixed two or more types of above-mentioned adhesives may be used as an adhesive agent, and the adhesive agent provided with both thermosetting property and ultraviolet-ray-curing property may be used.

<< Application of organic electroluminescence element >>
Since the organic EL element 101 is a surface light emitter as described above, it can be used as various light emission sources. For example, lighting devices such as home lighting and interior lighting, backlights for clocks and liquid crystals, lighting for billboard advertisements, light sources for traffic lights, light sources for optical storage media, light sources for electrophotographic copying machines, light sources for optical communication processors, Examples include a light source of an optical sensor. Moreover, it is not limited to these light emission light sources, It can use also as another light source.

  In particular, it can be effectively used for a backlight of a liquid crystal display device combined with a color filter and a light source for illumination.

  The organic EL element 101 may be used as a kind of lamp for illumination or exposure light source, a projection device that projects an image, or a display device that directly recognizes a still image or a moving image. (Display) may be used. In this case, with the recent increase in the size of lighting devices and displays, the light emitting surface may be enlarged by so-called tiling, in which the light emitting panels provided with the organic EL elements 101 are joined together in a plane.

  A driving method when used as a display device for reproducing a moving image may be a simple matrix (passive matrix) method or an active matrix method. In addition, a color or full-color display device can be manufactured by using two or more kinds of organic EL elements 10 having different emission colors.

<< Method for Manufacturing Organic Electroluminescent Element >>
As an example of the method for manufacturing the organic EL element of the present invention, a method for manufacturing the organic EL element 101 shown in FIG. 8 will be described.

  First, the 1st electrode 116 is formed on the gas barrier layer 5 of the gas barrier film 1 of this invention produced by the above-mentioned method. The first electrode 116 is formed from a transparent conductive material. For example, an electrode having a thickness of about 3 to 15 nm mainly composed of silver or a transparent conductive material such as ITO of about 100 nm is formed. As a method for forming the first electrode 116, for example, a spin coating method, a casting method, an ink jet method, a vapor deposition method, a sputtering method, a printing method, or the like can be used. The vacuum deposition method is particularly preferable from the viewpoint of difficulty in formation. In addition, before and after the formation of the first electrode 116, an auxiliary electrode pattern is formed as necessary.

Next, a hole injection layer 117a, a hole transport layer 117b, a light emitting layer 117c, an electron transport layer 117d, and an electron injection layer 117e are formed in this order, and an organic functional layer 117 is formed. As a method for forming each of these layers, for example, a spin coating method, a casting method, an ink jet method, a vapor deposition method, a sputtering method, a printing method, or the like can be used, but a homogeneous layer is easily obtained and a pinhole is generated. From the standpoint of difficulty, it is particularly preferable to use vacuum deposition or spin coating. Furthermore, different formation methods may be used for each layer. When employing a vapor deposition method for forming each of these layers, the vapor deposition conditions vary depending on the type of compound used, etc., but generally the boat heating temperature storing the compound is 50 to 450 ° C., and the degree of vacuum is 1 × 10 ⁻⁶ to 1 ×. It is desirable to appropriately select each condition in the range of 10 ⁻² Pa, vapor deposition rate of 0.01 to 50 nm / second, substrate temperature of −50 to 300 ° C., and thickness of 0.1 to 5 μm.

  Next, the second electrode 118 serving as a cathode is formed by an appropriate formation method such as an evaporation method or a sputtering method. At this time, the organic functional layer 117 is formed in a pattern in which a terminal portion is drawn from the upper side of the organic functional layer 117 to the periphery of the gas barrier film 1 while maintaining an insulating state with respect to the first electrode 116.

  Next, the first electrode 116, the organic functional layer 117, and the second electrode 118 provided on the gas barrier film 1 are solid-sealed. A sealing resin layer 119 is formed on one surface of the sealing member 120. Then, the surface of the sealing member 120 where the sealing resin layer 119 is formed is arranged so that the end portions of the lead wires of the first electrode 116 and the second electrode 118 come out of the sealing resin layer 119. The organic functional layer 117 and the second electrode 118 are overlaid on the gas barrier film 1. After superimposing the gas barrier film 1 and the sealing member 120, pressure is applied to the gas barrier film 1 and the sealing member 120. Further, in order to cure the sealing resin layer 119, the sealing resin layer 119 is heated. At this time, the sealing resin layer 119 is sufficiently cured so that there is no problem in the adhesion between the gas barrier layer 5 and the sealing resin layer 119.

  As described above, the organic EL element 101 solid-sealed with the gas barrier film 1 provided with the clear hard coat layer 4 and the gas barrier layer 5 on the film substrate 2 is obtained. In the production of such an organic EL element 101, it is preferable to produce the first electrode 116 to the second electrode 118 consistently by a single evacuation, but a different formation method is used by taking out from the vacuum atmosphere in the middle. May be. At that time, it is necessary to consider that the work is performed in a dry inert gas atmosphere.

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

<< Production of gas barrier film >>
[Preparation of gas barrier film 1]
(Preparation of film substrate)
As a film substrate, a transparent biaxially stretched polyethylene terephthalate film (KEL86W 125 μm, manufactured by Teijin DuPont Films Ltd., abbreviated as PET in Table 1) was prepared.

(Surface treatment of film substrate)
The prepared PET film surface was subjected to corona treatment. AGI-080 manufactured by Kasuga Denki Co., Ltd. was used as the corona discharge device, the gap between the discharge-like electrode of the corona discharge treatment device and the PET surface was set to 1 mm, and the surface corona for 10 seconds under the condition of a treatment output of 600 mW / cm ^2. Processed.

(Formation of clear hard coat layer)
Next, a UV-curable resin-containing coating solution (purple UV-1700B manufactured by Nippon Synthetic Chemical Co., Ltd.) mainly composed of polyurethane acrylate and acrylic ester is dried on a PET film subjected to corona treatment using a wet coater. After coating to a film thickness of 4 μm, drying was performed at 80 ° C. for 3 minutes. Next, the dried coating film was cured under a condition of 1.0 J / cm ² using a high-pressure mercury lamp in the atmosphere to form a clear hard coat layer.

(Formation of gas barrier layer)
Next, a gas barrier layer was formed on the clear hard coat layer according to the following method.

  Using a discharge plasma processing apparatus (hereinafter referred to as a plasma CVD method) capable of forming a discharge space between the rollers to which the magnetic field shown in FIG. 7 is applied to the PET film on which the clear hard coat layer is formed. A PET film having the above clear hard coat layer is attached as the film substrate 2, and a gas barrier layer is formed with a thickness of 300 nm on the clear hard coat layer of the PET film under the following film forming conditions (plasma CVD conditions). And the gas barrier film 1 of the comparative example was produced.

<Film formation conditions>
Supply amount of raw material gas (HMDSO): 50 sccm (Standard Cubic Centimeter per Minute)
Supply amount of oxygen gas (O ₂ ): 500 sccm
Degree of vacuum in the vacuum chamber: 3Pa
Applied power from the power source for plasma generation: 1.2 kW
Frequency of power source for plasma generation: 80 kHz
Film transport speed: 0.5 m / min
[Preparation of gas barrier film 2]
In the production of the gas barrier film 1, the surface of the film base was the same except that the following cycloolefin polymer film (abbreviated as COP1 in Table 1) was used instead of the PET film as the film base. A gas barrier film 2 having been subjected to corona treatment was prepared.

COP1: cycloolefin polymer film, manufactured by Nippon Zeon Co., Ltd., Zeonea ZF14 film, film thickness: 100 μm
[Preparation of gas barrier film 3]
In the production of the gas barrier film 1, the surface treatment of the PET film was replaced with a corona treatment, except that an excimer light treatment was performed using a vacuum ultraviolet irradiation apparatus having the configuration shown in FIG. 3. A gas barrier film 3 was prepared.

<Excimer light treatment on film substrate surface>
Ultraviolet irradiation device: excimer light irradiation device manufactured by M.D.COM MODEL: MECL-M-1-200
Irradiation wavelength: 172 nm
Lamp filled gas: Xe
Excimer lamp light intensity: 130 mW / cm ² (172 nm)
Distance between sample and light source: 1mm
Heating temperature of film substrate: 70 ° C
Oxygen concentration in the irradiation device: 1.0%
[Preparation of gas barrier film 4]
In the production of the gas barrier film 2, instead of COP 1, as shown in 2) of the surface opposite to the surface on which COP 1 is subjected to corona treatment, the following heat resistant laminate member was applied. A gas barrier film 4 was produced in the same manner except that COP2 was used.

  As shown in FIG. 2, the heat-resistant laminate member was applied to the COP film before the corona discharge treatment.

Heat-resistant laminate material: manufactured by Fujimori Kogyo Co., Ltd., heat-resistant protective film: Masutac PC PC-542PA
[Preparation of gas barrier film 5]
In the production of the gas barrier film 4, the surface treatment of the film substrate is replaced with the corona treatment, and the excimer light treatment used for the production of the gas barrier film 3 is applied in the same manner. 5 was produced.

[Preparation of gas barrier film 6]
A gas barrier film 6 was produced in the same manner as in the production of the gas barrier film 5 except that the clear hard coat layer was removed.

[Preparation of gas barrier film 7]
In the production of the gas barrier film 5, a gas barrier film 7 was produced in the same manner except that the following COC having a heat resistant laminate member was used instead of the COP 2 having the heat resistant laminate member.

COC: cycloolefin copolymer film, manufactured by Polyplastics, TOPAS 8007F-04 Film thickness: 70 μm
[Preparation of gas barrier film 8]
In the production of the gas barrier film 5, a gas barrier film 8 was produced in the same manner except that COP1 having no heat resistant laminate member was used instead of COP2 provided with the heat resistant laminate member.

[Preparation of gas barrier film 9]
In the production of the gas barrier film 5, the gas barrier film 9 was produced in the same manner except that the film thickness of the COP2 provided with the heat-resistant laminate member as the film substrate was changed from 100 μm to 35 μm.

[Production of Gas Barrier Film 10]
In the production of the gas barrier film 5, the gas barrier film 10 was produced in the same manner except that the film thickness of the COP2 provided with the heat-resistant laminate member as a film substrate was changed from 100 μm to 140 μm.

[Preparation of gas barrier film 11]
A gas barrier film 11 was produced in the same manner as in the production of the gas barrier film 5 except that the film thickness of the clear hard coat layer was changed from 4 μm to 10 μm.

[Production of gas barrier film 12]
A gas barrier film 12 was produced in the same manner as in the production of the gas barrier film 5 except that the film thickness of the clear hard coat layer was changed from 4 μm to 15 μm.

[Production of gas barrier film 13]
In the production of the gas barrier film 5, the gas barrier film 13 was formed in the same manner except that the gas barrier layer was formed by a wet coating method using polysilazane shown below instead of the plasma CVD method. Produced.

<Wet coating method using polysilazane>
As a polysilazane-containing coating solution, a 10% by mass dibutyl ether solution of perhydropolysilazane (PHPS; Aquamica NN120-10, non-catalytic type, manufactured by AZ Electronic Materials Co., Ltd.) was prepared.

  The prepared polysilazane-containing coating solution is coated on the clear hard coat layer with a wireless bar so that the average layer thickness after drying is 300 nm, and treated for 1 minute in an atmosphere of temperature 85 ° C. and humidity 55% RH. And dried. Further, the coating film containing polysilazane was formed by holding for 10 minutes in an atmosphere of temperature 25 ° C. and humidity 10% RH (dew point temperature −8 ° C.) for 10 minutes.

  The film base material (COP2) on which the coating film is formed is fixed on the operation stage 204 shown in FIG. 3, and the excimer light irradiation treatment is performed on the clear hard coat layer using the ultraviolet device 7 below under the following conditions. A coating type gas barrier layer was formed.

Ultraviolet irradiation device: excimer light irradiation device manufactured by M.D.COM MODEL: MECL-M-1-200
Irradiation wavelength: 172 nm
Lamp filled gas: Xe
Excimer lamp light intensity: 130 mW / cm ² (172 nm)
Distance between sample and light source: 1mm
Stage heating temperature: 70 ° C
Oxygen concentration in the irradiation device: 1.0%
Excimer lamp irradiation time: 5 seconds In the preparation of each gas barrier film, details of each component described in Table 1 with the abbreviations are as follows.

<Fill base material>
PET: Biaxially stretched polyethylene terephthalate film (KEL86W 125 μm, manufactured by Teijin DuPont Films Co., Ltd., surface corona treatment COP1: Cycloolefin polymer film, manufactured by Nippon Zeon Co., Ltd., Zeonea ZF14 film, film thickness: 100 μm, surface corona treatment COP2: cycloolefin polymer film, ZEON Corporation, ZEONEA ZF14 film, film thickness: 100 μm, surface excimer light treatment COP3: cycloolefin polymer film, ZEON Corporation, ZEONEA ZF14 film, film thickness: 35 μm, surface excimer light treatment COP4: cycloolefin polymer film, ZEON Zonea ZF14 film, 140 μm, surface excimer light treatment COC: cycloolefin copolymer film, manufactured by Polyplastics , TOPAS 8007F-04 Film thickness: 70 μm, surface excimer light treatment <Gas barrier layer formation method>
Plasma CVD method: Discharge plasma treatment capable of forming a discharge space between rollers to which the magnetic field shown in FIG. 7 is applied Wet coating method: Using polysilazane, reforming treatment by excimer light irradiation to form a gas barrier layer Method << Production of Organic EL Element >>
Next, organic EL elements 101 to 113 were produced using the produced gas barrier films 1 to 13 according to the following method. In the production of each organic EL element described below, among the gas barrier films to be used, a film having a heat-resistant laminate member on the back side was used in a form in which it was removed in advance.

  Each gas barrier film was fixed to a substrate holder of a commercially available vacuum deposition apparatus, and the following compound No. 10 was put in a resistance heating boat made of tungsten, and the gas barrier film holder and the heating boat were mounted in a first vacuum chamber of a vacuum deposition apparatus. Moreover, silver (Ag) was put into the resistance heating boat made from tungsten, and it attached in the 2nd vacuum chamber of a vacuum evaporation system.

After depressurizing the first vacuum chamber of the vacuum deposition apparatus to 4 × 10 ⁻⁴ Pa, Compound No. The heating boat containing 10 was energized and heated, and the underlayer of the first electrode was provided with a layer thickness of 10 nm at a deposition rate of 0.1 to 0.2 nm / second. The gas barrier film on which the underlayer was formed was transferred to the second vacuum chamber while being vacuumed, and after the pressure in the second vacuum chamber was reduced to 4 × 10 ⁻⁴ Pa, the heating boat containing silver was energized and heated. As a result, a first electrode made of silver having a thickness of 8 nm was formed at a deposition rate of 0.1 to 0.2 nm / second.

Next, after reducing the pressure to 1 × 10 ⁻⁴ Pa using a commercially available vacuum deposition apparatus, the following compound HT-1 was deposited on the formed first electrode while moving the gas barrier film. Vapor deposition was performed at 0.1 nm / second, and a 20 nm hole transport layer (HTL) was provided.

  Next, using the following compound A-3 (blue light emitting dopant), the following compound A-1 (green light emitting dopant), the following compound A-2 (red light emitting dopant) and the following compound H-1 (host compound), a compound A -3 changes the deposition rate so that the content rate is linear with respect to the layer thickness direction and the gradient is 35% to 5%, and the compound A-1 and the compound A-2 do not depend on the layer thickness. At a deposition rate of 0.0002 nm / second, the compound H-1 has a gradient concentration of 64.6% to 94.6% in the layer thickness direction so that each concentration is constant at 0.2% by mass. The vapor deposition rate was changed so that a co-deposited light emitting layer having a layer thickness of 70 nm was formed.

  Then, the following compound ET-1 was vapor-deposited on the light emitting layer to form an electron transport layer with a layer thickness of 30 nm, and further potassium fluoride (KF) was vapor-deposited to form an electron injection layer with a layer thickness of 2 nm. Furthermore, aluminum was vapor-deposited to form a second electrode having a layer thickness of 110 nm.

  In addition, the compound No. used for the formation of each organic functional layer was used. 10, Compound HT-1, Compound A-1 to Compound 3, Compound H-1, and Compound ET-1 are compounds shown below.

  Next, an aluminum foil with a thickness of 25 μm is used as a sealing member, and a thermosetting sheet adhesive (epoxy resin) is bonded as a sealing resin layer on one surface of the aluminum foil with a thickness of 20 μm. Using the stop member, the resin base material prepared up to the second electrode was superposed. At this time, the adhesive forming surface of the sealing member and the organic functional layer surface of the element were continuously overlapped so that the ends of the lead wires of the first electrode and the second electrode were exposed.

  Next, the sample containing the gas barrier film was placed in a decompression device, and held for 5 minutes under a reduced pressure condition of 90 ° C. and 0.1 MPa with pressure applied to the stacked sample and the sealing member. . Subsequently, the sample including the gas barrier film was returned to the atmospheric pressure environment, and further heated at 120 ° C. for 30 minutes to cure the adhesive.

  The sealing step is performed under atmospheric pressure and in a nitrogen atmosphere with a moisture content of 1 ppm or less, in accordance with JIS B 9920, with a measured cleanliness of class 100, a dew point temperature of −80 ° C. or less, and an oxygen concentration of 0.8 ppm or less. At atmospheric pressure.

  The organic EL elements 101 to 113 were produced through the above steps. The area of the light emitting region was set to 5 cm × 5 cm.

<< Evaluation of gas barrier film and organic EL element >>
[Evaluation of gas barrier film]
(Durability evaluation: Measurement of water vapor permeability after bending treatment)
About each produced gas-barrier film, the water vapor transmission rate 1 (g / m < ² > * day, unprocessed) in 38 degreeC and 90% RH using MOCON water vapor permeability measuring apparatus PERMATRAN-W made from MOCON. It was measured. Next, each gas barrier film was subjected to the same water vapor permeability 2 (g / m ² · day, treated) after storage for 1 week in an environment of 50 ° C. and 80% RH.

Next, the rate of increase in water vapor permeability 2 (g / m ² · day) of the sample treated in a high-temperature and high-humidity environment relative to water vapor permeability 1 (g / m ² · day) of the untreated sample (water vapor permeability 2 / Water vapor permeability 1) was calculated, and durability (retention property of gas barrier performance) was evaluated according to the following criteria.

5: Increase rate of water vapor permeability is less than 1.10 times 4: Increase rate of water vapor permeability is 1.10 times or more and less than 1.50 times 3: Increase rate of water vapor permeability is 1.50 times or more and less than 2.00 times 2: Increase rate of water vapor permeability is 2.00 times or more and less than 2.50 times 1: Increase rate of water vapor permeability is 2.50 times (Evaluation of flatness)
Using the CNC image measuring machine Quick Vision QVH404 (made by Mitutoyo Corporation) as a flatness measuring device, the flatness of the sample prepared by the above durability evaluation and stored for 1 week in an environment of 50 ° C. and 80% RH is measured. The planarity was evaluated according to the following criteria.

5: Flatness is less than 0.05 mm 4: Flatness is 0.05 mm or more and less than 0.10 mm 3: Flatness is 0.10 mm or more and less than 0.5 mm 2: Flatness is 0.50 mm or more and less than 1.0 mm 1: Flatness is 1.0 mm or more [Evaluation of Organic EL Element]
About the said organic EL elements 101-113, the electric current of 1 mA / cm < ² > was applied and it was made to light-emit. Next, as for the light emission state immediately after application and after continuous light emission for 300 hours and 500 hours as the light emission time in an environment of 50 ° C. and 80% RH, a 100 × optical microscope (MS-804, manufactured by Moritex Corporation) A part of the organic EL element was magnified and photographed with a lens MP-ZE25-200). Next, the photographed image was cut out in a 2 mm square, and the presence or absence of dark spots was observed for each image. From the observation results, the ratio of the dark spot generation area to the light emission area was determined, and the dark spot resistance was evaluated according to the following criteria.

5: No dark spots are observed even after 500 hours of light emission. 4: Dark spots are not observed even after 300 hours of light emission, but slightly after 500 hours of light emission. Generation of dark spots is observed (generation area 0.1% or more, less than 3.0%)
3: Slight dark spots are observed in the sample after 300 hours of light emission (generation area 0.1% or more and less than 3.0%)
2: Generation of clear dark spots is observed in the sample after 300 hours of light emission (generation area of 3.0% or more and less than 6.0%)
1: A large number of dark spots are observed in the sample after luminescence for 300 hours (generation area of 6.0% or more).
The results obtained as described above are shown in Table 1.

  As is clear from the results shown in Table 1, the gas barrier film produced by the method defined in the present invention is different from the comparative example even when stored for a long time in a high temperature and high humidity environment. There was no deterioration in adhesion, and excellent gas barrier properties and flatness could be maintained. Moreover, it turns out that generation | occurrence | production of the dark spot resulting from film | membrane peeling etc. in a high-temperature, high-humidity environment is suppressed by providing an organic EL element with the gas barrier film provided with such a characteristic.

DESCRIPTION OF SYMBOLS 1 Gas barrier film 2 Film base material 3 Surface modification area | region 4A Clear hard-coat layer (uncured)
4 Clear hard coat layer 5 Gas barrier layer 6 Heat resistant laminate member 7 Vacuum ultraviolet irradiation device (excimer light irradiation device)
DESCRIPTION OF SYMBOLS 8 Holder 9 Excimer light irradiation apparatus 11 Sending roller 21, 22, 23, 24 Conveyance roller 30 Discharge plasma processing apparatus 31, 32 Film-forming roller 41 Gas supply pipe 51 Power supply 61, 62 Magnetic field generator 71 Winding roller 101 Organic EL
116 1st electrode element 117 Organic functional layer 117a Hole injection layer 117b Hole transport layer 117c Light emitting layer 117d Electron transport layer 117e Electron injection layer 118 Second electrode 119 Sealing resin layer 120 Sealing member 201 Device chamber 204 Sample stage 206 Light-shielding plate h Emitted light L Excimer light

Claims (6)

Step A for hydrophilizing the surface of a film substrate mainly composed of a cycloolefin polymer or a cycloolefin copolymer by subjecting it to a vacuum ultraviolet ray irradiation treatment,
Step B of forming a clear hard coat layer by applying a clear hard coat layer coating solution on the hydrophilic surface of the film base,
Step C for applying a curing treatment to the clear hard coat layer,
And Step D of forming a gas barrier layer on the cured clear hard coat layer,
A method for producing a gas barrier film, characterized by being manufactured through the process.   2. The gas according to claim 1, wherein before the step C, a step E of providing a heat-resistant laminate member is provided on the surface of the film base opposite to the surface subjected to the vacuum ultraviolet irradiation treatment. A method for producing a barrier film.   The method for producing a gas barrier film according to claim 1, wherein the gas barrier layer is formed by a chemical vapor deposition method (CVD method).   The method for producing a gas barrier film according to claim 3, wherein the chemical vapor deposition method used for forming the gas barrier layer is a discharge plasma chemical vapor deposition method.   The film thickness of the said film base material exists in the range of 30-150 micrometers, The manufacturing method of the gas barrier film as described in any one of Claim 1- Claim 4 characterized by the above-mentioned.   The layer thickness of the said clear hard-coat layer exists in the range of 1-10 micrometers, The manufacturing method of the gas barrier film as described in any one of Claim 1-5 characterized by the above-mentioned.

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