JP2005319744A - Gas barrier laminate and light emitting element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To form a gas barrier laminate using an organic film hard to cause peeling or the flaw accompanied by the peeling at the interface with an inorganic film, enhanced in adhesion and extremely low in degassing. <P>SOLUTION: In the gas barrier laminate of the inorganic film and the organic film both of which are formed on one side or both sides of a transparent resin substrate, as the organic film, a perfluorocarbon decomposed matter film containing an element or a metal compound is used. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a gas barrier laminate and a light emitting device, and more specifically, a gas barrier laminate excellent in impermeability to water vapor, oxygen, etc., which is formed by laminating at least one inorganic film and at least one organic film, and The present invention relates to a light-emitting element using the laminate.

  A gas barrier film in which a gas barrier layer is formed on a transparent resin film substrate has been used as a packaging material for food and medicine. Recently, it has been attracting attention as a base material for electronics devices due to its thinness, lightness and flexibility. Particularly for liquid crystal and organic electroluminescence display substrates, resin film substrates are expected for wall-mounted TV and electronic paper applications. In this case, the resin film base material is required to have a higher gas barrier property, particularly a water vapor barrier property than conventional packaging materials.

Conventionally, a single layer film of an inorganic oxide such as SiO ₂ or Al ₂ O ₃ has been mainly used as a gas barrier layer. However, when the film thickness is thin, the gas barrier property is not sufficiently exhibited. On the other hand, when the film thickness is increased, the internal stress increases and the film warps. There was something to do.

  It has been reported that a laminate of an organic film and an inorganic film has high gas barrier properties (Japanese Patent No. 2999616, Japanese Patent Application Laid-Open Nos. 2004-1296, 2003-206361, 2003-48271, etc.). According to this report, by laminating an organic film and an inorganic film, the organic film has a gas barrier property, and the organic film formed on the resin film substrate compensates for unevenness on the substrate surface and is smooth. Therefore, an inorganic film can be densely formed on the surface, resulting in a thin laminate having a high gas barrier property. Moreover, since internal stress can be relieved, it is reported that a very high gas barrier property can be obtained because cracks are hardly generated in the inorganic film.

  An acrylic resin is used as a material for the organic film when the laminate is formed. However, as a result of our study, it was found that the acrylic resin has low adhesion to the inorganic film. For this reason, peeling and defects accompanying peeling are likely to occur at the interface, and as a result, gas barrier properties may be deteriorated. Furthermore, the acrylic resin has a high water absorption rate and volatilization of water vapor or the like occurs. As a result, the film density of the inorganic film formed on the resin tends to be low. Theoretically, in order to develop a high gas barrier property, the number of laminated inorganic films must be increased, but this is technically difficult.

  On the other hand, it has been proposed to use a fluorine compound polymer as an organic film of the laminate (Japanese Patent Laid-Open No. 2003-340955). However, the fluorine compound polymer has extremely low adhesion to the inorganic film.

  In addition, the present applicant has filed an invention relating to a method for efficiently producing a sealing film for an organic EL device comprising a perfluoroolefin decomposition polymer by plasma CVD under discharge dissociation conditions (Japanese Patent Laid-Open No. 2002). -056771). However, further improvements are required in adhesion to the substrate and gas barrier properties.

Japanese Patent No. 2999616 JP 2004-1296 A JP 2003-206361 A JP 2003-48271 A JP 2003-340955 A JP 2002-056771 A

  The object of the present invention is to provide high adhesion at the interface between an inorganic film and an organic film, hardly cause defects due to peeling and peeling, increase the number of laminated inorganic films and organic films, and have a high gas barrier property. Is to form the body.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have used a perfluoroolefin decomposition polymer as an organic film in a sealing film composed of a laminate of an inorganic film and an organic film. It has been found that a gas barrier laminate having high gas barrier properties and high adhesion to an inorganic film can be formed while being a compound polymer, and the present invention has been accomplished.
Thus, according to the present invention,
1. A laminate comprising a sealing film in which at least one organic film and at least one inorganic film are laminated, and a transparent resin film substrate, wherein the organic film is formed of a perfluoroolefin decomposition polymer. A gas barrier laminate characterized by that.
2. The gas barrier laminate as described above, wherein the organic film is formed by introducing perfluoroolefin in a gaseous state under vacuum.
3. The gas barrier laminate, wherein the inorganic film is a metal or metalloid compound formed under vacuum.
4). The gas barrier laminate according to claim 1, wherein the water absorption of the organic film is 0.1% by weight or less.
5. The gas barrier laminate described above, wherein the light transmittance at a wavelength of 550 nm is 70% or more.
6). A sealing film in which at least one organic film and at least one inorganic film are laminated on a circuit board in which a lower electrode layer, a light emitting material layer, and an upper electrode layer are sequentially laminated on at least one of the substrates. And the organic film is formed of a perfluoroolefin decomposition polymer.
7. A light-emitting element obtained by sealing a circuit board, in which a lower electrode layer, a light emitting material layer, and an upper electrode layer are sequentially formed on at least one of the substrates, with the gas barrier laminate.

 The gas barrier laminate of the present invention is a laminate film that is excellent in adhesiveness by introducing a perfluoroolefin decomposition polymer into an organic film, and moreover, a stronger film is obtained, and is excellent in water vapor barrier properties and gas barrier properties. Can be provided. This laminate can be suitably used as a gas barrier layer of a liquid crystal or organic EL display substrate.

 The gas barrier laminate of the present invention is a laminate comprising a sealing film in which at least one organic film and at least one inorganic film are laminated, and a transparent resin film substrate, wherein the organic film is a perfluoroolefin. It is a gas barrier laminate characterized by being a decomposition polymer.

  The gas barrier laminate of the present invention is formed by laminating a sealing film in which at least one organic film and at least one inorganic film are laminated on one side or both sides of a transparent resin film substrate. The number of layers of the organic film and the inorganic film may be the same or more, but one in which both are alternately laminated is preferable.

  The film in contact with the resin film substrate may be an organic film or an inorganic film, but if the organic film is in contact with the resin film substrate, the surface of the resin film substrate may be uneven. Since an organic film is formed on the surface, the surface becomes smooth. Therefore, an inorganic film formed on the organic film is preferable because it becomes a dense and smooth film without defects and has high gas barrier properties.

 In this embodiment, even if the resin film substrate is subjected to external force, it is relaxed by the organic film, so that the inorganic film is not easily cracked, and high gas barrier properties are maintained for a long time.

The perfluoroolefin decomposition polymer which comprises an organic film about an organic film is a polymer which used perfluoroolefin as a raw material. The polymer is not particularly limited as long as it is a polymer that can form an organic film.

Such a perfluoroolefin is a compound composed of only a carbon atom and a fluorine atom and having a double bond or a triple bond.
The carbon number is preferably 2 to 7, more preferably 2 to 5, still more preferably 4 to 5, and particularly preferably 5.

  Specific examples of the perfluoroolefin compound include a perfluoroolefin compound having 2 carbon atoms such as tetrafluoroethylene; a perfluoroolefin compound having 3 carbon atoms such as hexafluoropropene, tetrafluoropropyne, and tetrafluorocyclopropene. Hexafluoro-2-butyne, hexafluoro-1-butyne, hexafluorocyclobutene, hexafluoro-1,3-butadiene, hexafluoro- (1-methylcyclopropene), octafluoro-1-butene, octafluoro- Perfluoroolefin compounds having 4 carbon atoms such as 2-butene; octafluoro-1-pentyne, octafluoro-2-pentyne, octafluoro-1,3-pentadiene, octafluoro-1,4-pentadiene, octafluorocyclopentene , Octafluoro Perfluoroolefin compounds having 5 carbon atoms such as soprene, hexafluorovinylacetylene, octafluoro- (1-methylcyclobutene), octafluoro- (1,2-dimethylcyclopropene); dodecafluoro-1-hexene, dodeca Fluoro-2-hexene, dodecafluoro-3-hexene, decafluoro-1,3-hexadiene, decafluoro-1,4-hexadiene, decafluoro-1,5-hexadiene, decafluoro-2,4-hexadiene, deca Perfluoroolefins having 6 carbon atoms such as fluorocyclohexene, hexafluorobenzene, octafluoro-2-hexyne, octafluoro-3-hexyne, octafluorocyclo-1,3-hexadiene, octafluorocyclo-1,4-hexadiene Compound; undecafluoro-1-heptene, unde Fluoro-2-heptene, undecafluoro-3-heptene, perfluoro-olefin carbon number compounds, such as dodecafluoro triazabenzocycloheptene 7; it can be mentioned,

  Tetrafluoroethylene, hexafluoropropene, tetrafluoropropyne, tetrafluorocyclopropene, hexafluoro-2-butyne, hexafluoro-1-butyne, hexafluorocyclobutene, hexafluoro-1,3-butadiene, hexafluoro- ( 1-methylcyclopropene), octafluoro-1-butene, octafluoro-2-butene, octafluoro-1-pentyne, octafluoro-2-pentyne, octafluoro-1,3-pentadiene, octafluoro-1,4 -Pentadiene, octafluorocyclopentene, octafluoroisoprene, hexafluorovinylacetylene, octafluoro-1-methylcyclobutene, octafluoro-1,2-dimethylcyclopropene are preferred,

  Hexafluoro-2-butyne, hexafluoro-1-butyne, hexafluorocyclobutene, hexafluoro-1,3-butadiene, hexafluoro- (1-methylcyclopropene), octafluoro-1-butene, octafluoro-2 -Butene, Octafluoro-1-pentyne, Octafluoro-2-pentyne, Octafluoro-1,3-pentadiene, Octafluoro-1,4-pentadiene, Octafluorocyclopentene, Octafluoroisoprene, Hexafluorovinylacetylene, Octafluoro -(1-methylcyclobutene) and octafluoro- (1,2-dimethylcyclopropene) are more preferable,

  Octafluoro-2-pentyne, octafluoro-1,3-pentadiene and octafluorocyclopentene are more preferred, octafluoro-2-pentyne and octafluorocyclopentene are particularly preferred, and octafluoro-2-pentyne is particularly preferred.

  In order to improve the adhesion to the inorganic film, an inorganic compound containing a fluorine atom can be used during film formation and can be contained in the organic film.

Examples of the inorganic compound containing a fluorine atom include fluorides of alkali metals and alkaline earth metal elements, and examples thereof include BaF ₂ , CaF ₂ , MgF ₂ , and LiF. The amount of the inorganic compound containing a fluorine atom is preferably 20% by weight or less, more preferably 10% by weight or less based on the whole fluorine compound.

 Further, in order to improve the adhesion to the inorganic film, a compound containing silicon can be used in the film formation and can be contained in the organic film.

Examples of silicon-containing compounds include organic monosilane compounds such as tetramethoxysilane, tetraethoxysilane, and methyltrimethoxysilane; organic polysilane compounds such as hexamethyldisilane, 1,2-diphenyltetramethyldisilane, and hexamethoxydisilane; And organic siloxane compounds such as siloxane and tetramethyldisiloxane; organic silazane compounds such as tetramethyldisilazane and hexamethyldisilazane;
The amount of the silicon-containing compound used is preferably 20% by weight or less, more preferably 10% by weight or less based on the entire fluorine compound.

 A dry manufacturing method is optimal as a method for manufacturing the organic film. Dry production methods such as vapor deposition, CVD (chemical vapor deposition) and sputtering are preferred, and CVD is particularly preferred. In the CVD method, a gas using a fluorine compound as a raw material is introduced into a vacuum, and the substrate is heated, plasma, an ion beam, a laser assisted CVD, or the like.

 The method of the plasma CVD method is not particularly limited, and for example, the method described in JP-A-9-237783 can be employed. As a device used for plasma CVD, a parallel plate type CVD device is usually used. A microwave CVD apparatus, an ECR-CVD apparatus, a high-density plasma CVD apparatus (helicon wave plasma, inductively coupled plasma), or the like can also be used.

 The thickness of the organic film is not particularly limited as long as the subject can be achieved, but it is preferably 0.01 to 3.0 μm, preferably 0.03 to 1.0 μm. If it is thin, the adhesion to the inorganic film and the gas barrier property tend to be low. On the other hand, if it is thick, the total light transmittance tends to decrease.

Regarding the inorganic film The inorganic film used in the present invention is an inorganic film conventionally known as a gas barrier film. The element constituting the inorganic film is not particularly limited as long as it is a metal or a semimetal that can impart gas barrier properties. Specific examples include Si, Mg, Ti, Al, In, Sn, Zn, W, Ce, and Zr. Metal oxides, nitrides, nitrogen oxides, sulfides, and the like are preferable as raw materials, and good films Of these, silicon oxide SiOx and silicon nitride SiNx are more preferable. x is preferably 1 to 4.

 The method for producing the inorganic film is not particularly limited, but a vacuum deposition method, a sputtering method, a CVD method is used in that it has a crystal structure, that is, a film made of an inorganic compound having a high film density can be efficiently formed. The vacuum deposition method and the CVD method using arc discharge plasma are particularly preferable in that there is no damage to the film or the film substrate and the film density can be increased.

  The thickness of the inorganic film is not particularly limited, but is preferably 10 nm to 500 nm, and more preferably 30 to 400 nm. When the thickness of the inorganic film is 10 nm or less, the inorganic compound tends to be formed as island-like deposits, so that the gas barrier property may be insufficient. On the other hand, when the thickness is 500 nm or more, the internal stress in the film increases, and the warpage of the laminate tends to occur.

 In the present invention, the crystalline state of the inorganic film is preferably a uniform amorphous structure that does not include a columnar structure or a granular structure. When the columnar structure or the granular structure is included, the crystal grain boundary becomes a gas molecule diffusion path, and the gas barrier property may be insufficient.

  The laminated structure in the sealing film of the gas barrier laminate of the present invention is not particularly limited as long as the inorganic film and the organic film are laminated one or more layers, but in order to further exert the effects of the invention. It is preferable that a plurality of inorganic films and organic films are alternately laminated. The thickness of the laminate is preferably 100 nm to 3 μm, more preferably 200 nm to 1 μm.

  The transparent resin film substrate used in the present invention is a film made of a transparent resin. Examples of the transparent resin include a polymer resin having an alicyclic structure, a chain olefin polymer such as polyethylene and polypropylene, a polycarbonate polymer, a polyester polymer, a polysulfone polymer, and a polyethersulfone polymer. It is not particularly limited as long as it is transparent and flexible like a polymer, polystyrene polymer, polyvinyl alcohol polymer, cellulose acetate polymer, polyvinyl chloride polymer, polymethacrylate polymer. . Among these, a polymer resin having an alicyclic structure having high transparency and low water absorption is preferable.

  The glass transition temperature of the transparent resin substrate used in the present invention is preferably 80 ° C. or higher, more preferably 100 to 250 ° C. A substrate made of a transparent resin having a glass transition temperature in such a range is excellent in durability without being deformed or stressed during use at high temperatures. The film thickness of the substrate is preferably 30 to 300 μm, more preferably 50 to 200 μm, from the viewpoint of mechanical strength and the like.

  The resin film substrate preferably has a volatile component content of 0.1% by weight or less, and more preferably 0.05% by weight or less. When the content of the volatile component is in the above range, the dimensional stability of the film is improved, and uneven stacking when an inorganic film or an organic film is stacked on the upper surface can be reduced.

The resin film substrate preferably has a saturated water absorption of 0.01% by weight or less, and more preferably 0.007% by weight or less. When the saturated water absorption exceeds 0.01% by weight, the adhesion between the layer made of an inorganic compound and other layers and the resin film substrate is lowered, and the layer tends to be peeled off during long-term use. Furthermore, there is a possibility that productivity and yield may be reduced due to the time required for evacuation due to moisture, or a layer made of an inorganic compound or other layers may be altered.
The saturated water absorption rate of the resin film substrate is measured according to JIS K7209.

  The resin film substrate may be an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet absorber, an antistatic agent, a dispersant, a chlorine scavenger, a flame retardant, a crystallization nucleating agent, or an antiblocking agent, if necessary. Antifogging agents, mold release agents, pigments, organic or inorganic fillers, neutralizing agents, lubricants, decomposition agents, metal deactivators, antifouling agents, antibacterial agents and other resins, thermoplastic elastomers, etc. A well-known additive can be contained in the range which does not impair the effect of invention. These additives are each usually added in an amount of 0 to 5 parts by weight, preferably 0 to 3 parts by weight, per 100 parts by weight of the thermoplastic resin.

  Examples of the method for producing the resin film substrate include a solution casting method and a melt extrusion molding method. Among these, the melt extrusion molding method is preferable because the content of volatile components in the resin film substrate and the thickness unevenness can be reduced. Further, examples of the melt extrusion molding method include a method using a die and an inflation method, but a method using a die, particularly a T die, is preferable in terms of excellent thickness accuracy and productivity.

  The film thickness of the resin film substrate is preferably 30 to 300 μm, more preferably 40 to 200 μm.

  As the transparency of the transparent resin film substrate used in the present invention, the total light transmittance based on ASTM D1003 is preferably 60% or more, more preferably 70% or more. If the total light transmittance is too small, it may be difficult to use for transparent purposes.

The gas barrier laminate of the present invention has an organic film and an inorganic film laminated on a transparent resin film substrate, has high adhesion at each interface, and has extremely high gas barrier properties, particularly water vapor barrier properties. Furthermore, since any of the resin film substrate, the organic film, and the inorganic film can have high transparency, it can be used for optical applications in addition to packaging applications.
For example, it can be suitably used for an organic EL light emitting device.

Next, the light emitting device of the present invention will be described. FIG. 1 shows a configuration example of a typical light emitting element. A light emitting element 801 shown in FIG. 1 is formed by sequentially laminating a resin base material 401, a lower electrode layer 501, a light emitting material layer 601, and an upper electrode layer 502.
The organic EL light-emitting element emits light by applying a direct-current voltage to the two electrodes, the anode and the cathode, so that holes and electrons are sent from the electrode to the light-emitting material layer. That is, when a voltage is applied to the lower electrode layer 501 and the upper electrode layer 502, the light emitting material layer 601 emits light.
The light emitting material layer 601 is easily deteriorated by water vapor, oxygen, or the like, and in order to extend the life of the organic EL light emitting element, it is indispensable to sufficiently seal the light emitting material layer 601 from water vapor or oxygen with a gas barrier film.

Examples of the material constituting the upper electrode layer 502 used in the light-emitting element of the present invention include a material for emitting light from the upper electrode layer. Specifically, a conductive metal oxide, a translucent metal, or a material thereof is used. A laminated body is mentioned. Specifically, indium oxide, zinc oxide, tin oxide, and their composite materials such as indium tin oxide (ITO), indium zinc oxide, etc., conductive glass (NESA, etc.), gold, platinum Silver, copper, etc. are used, and among them, ITO, indium / zinc / oxide, and tin oxide are preferable. As the upper electrode layer, an organic transparent conductive film such as polyaniline or a derivative thereof or polythiophene may be used.
The average thickness of the upper electrode layer can be appropriately selected in consideration of light transmittance and electrical conductivity, but is usually 10 nm to 10 μm, preferably 100 to 500 nm.

  In the light emitting device of the present invention, it is convenient that the upper electrode layer is transparent or translucent because the light emission is transmitted, and thus the light emission efficiency is good. Examples of the method for forming the upper electrode layer include a vacuum deposition method, a sputtering method, and a laminating method in which a metal thin film is thermocompression bonded.

There is no restriction | limiting in particular as a material which comprises the light emitting material layer 601 used for the light emitting element of this invention, A well-known thing can be used as a light emitting material in a conventional organic EL element. Specific examples of such light-emitting materials include fluorescent brighteners such as benzothiazole, benzimidazole, and benzoxazole, metal chelated oxinoid compounds, styrylbenzene compounds, distyrylpyrazine derivatives, and aromatic dimethylidine compounds. Etc.
The average thickness of the light-emitting material layer varies depending on the material used, and may be selected so that the drive voltage and the light emission efficiency are appropriate. For example, the average thickness is 1 nm to 1 μm, preferably 2 nm to 500 nm. .
In the light emitting device of the present invention, two or more kinds of light emitting materials may be mixed and used in the light emitting material layer, or two or more light emitting material layers may be laminated. Examples of the method for forming the light emitting material layer include a vacuum deposition method and a casting method.

As a material constituting the lower electrode layer 502 used in the light emitting element of the present invention, a material having a small work function is preferable, in order to reflect emitted light from the light emitting material layer toward the lower electrode layer and to direct toward the sealing layer. More preferably, it is a mirror body. Specifically, metals such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, And two or more alloys thereof, or an alloy of one or more of them and one or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin, graphite or graphite An intercalation compound or the like is used. Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, calcium-aluminum alloy, and the like. The lower electrode layer may have a laminated structure of two or more layers. Examples of the method for forming the lower electrode layer include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method.
The average thickness of the lower electrode layer can be appropriately selected in consideration of electric conductivity and durability, but is usually 10 nm to 10 μm, preferably 100 to 500 nm.

The light emitting element of the present invention may have other layers in addition to the transparent resin substrate 401, the lower electrode layer 501, the light emitting material layer 601, the upper electrode layer 502, and the sealing layers 200, 201, and 202. Good.
Examples of the other layers include a hole injection layer, a hole transport layer, an electron transport layer, and an electron injection layer.

  The hole injection layer is a layer provided adjacent to the lower electrode and refers to a layer having a function of improving hole injection efficiency from the lower electrode. The average thickness of the hole injection layer is usually 1 nm to 100 nm, preferably 2 nm to 50 nm.

  The hole transport layer refers to a layer having a function of transporting holes. The thickness of the hole transport layer differs depending on the material used and may be selected so that the drive voltage and the light emission efficiency are appropriate, but at least a thickness that does not cause pinholes is required. If the thickness is too thick, the driving voltage of the element increases, which is not preferable. Therefore, the average thickness of the hole transport layer is usually 1 nm to 1 μm, preferably 2 nm to 500 nm.

Examples of materials used for the hole injection layer and the hole transport layer include those conventionally known as hole transport compounds in organic EL devices.
The electron transport layer refers to a layer having a function of transporting electrons.

  The thickness of the electron transport layer varies depending on the material used, and may be selected so that the drive voltage and the light emission efficiency are moderate values, but at least a thickness that does not cause pinholes is required. If the thickness is too thick, the drive voltage of the element becomes high, which is not preferable. Therefore, the average thickness of the electron transport layer is usually 1 nm to 1 μm, preferably 2 nm to 500 nm.

The electron injection layer is a layer provided adjacent to the upper electrode layer and has a function of improving the electron injection efficiency from the upper electrode and has an effect of reducing the driving voltage of the element.
The average thickness of the electron injection layer is usually 1 nm to 100 nm, preferably 2 nm to 50 nm.

Examples of materials used for the electron transport layer and the electron injection layer include those conventionally known as electron transport compounds in organic EL devices.
Examples of methods for forming these other layers include spin coating, casting, and vacuum deposition.

Next, the gas barrier laminate of the present invention will be described.
2, 3 and 4 are cross-sectional views showing an example of the gas barrier laminate of the present invention. That is, the gas barrier laminates 200, 201, and 202 are formed of a sealing film formed by sequentially laminating a resin base material 400, an organic film, and an inorganic film. The organic film and the inorganic film were stacked using the plasma CVD method described above.
By covering and closely adhering the light emitting element with the laminate of the present invention, deterioration of the light emitting material layer due to water vapor or oxygen can be prevented.

 In the organic EL device of the present invention, it is preferable that a sealing layer is provided so as to cover the side surfaces of the lower electrode layer, the light emitting material layer, and the upper electrode layer, and it is more preferable to cover the transparent substrate. By providing the sealing layer as described above, moisture and gas entering from the side surface can be shielded. The method for sealing the laminated body is not particularly limited, and other than the dry manufacturing method, it may be sealed by close contact, specifically, a pressure bonding method, a thermocompression bonding method, an adhesive method, or the like.

 FIG. 5 shows an example of the light emitting device of the present invention. In the embodiment of the light emitting element of the present invention, a substrate 401, a lower electrode layer 501, a light emitting material layer 601, an upper electrode layer 502, and a sealing layer 52 are sequentially laminated. As a method for stacking the organic film and the inorganic film of the sealing layer 52, the plasma CVD method described above was used.

FIG. 6 is an example of a cross-sectional view of an example in which a circuit base material is formed on the substrate using the gas barrier laminate of the present invention as a substrate, and gas barrier properties are further imparted.
An embodiment of the light emitting device of the present invention includes a substrate 200 made of a gas barrier laminate, which is laminated using the plasma CVD method described above,
The lower electrode layer 501, the light emitting material layer 601, the upper electrode layer 502 and the sealing layer 52 are sequentially laminated.
As a method for stacking the organic film and the inorganic film of the sealing layer 52, the plasma CVD method described above was used.
By covering and closely adhering the light emitting element with the laminate of the present invention, it is possible to further prevent the light emitting material layer from being deteriorated by water vapor or oxygen.

FIG. 7 is a cross-sectional view of an example in which the gas barrier laminate 51 laminated in FIG. 3 of the present invention covers the light emitting element and is used as a sealing layer.
The embodiment of the light emitting device of the present invention has a structure in which the periphery is sealed with a sealing layer 51 on a circuit board 901. FIG. 7 shows an example in which the transparent substrate 401 and the sealing layer 51 are sealed with an adhesive 700.
By covering and closely adhering the light emitting element with the laminate of the present invention, deterioration of the light emitting material layer due to water vapor or oxygen can be prevented.

8 covers the light emitting element with the gas barrier laminate 51 laminated in FIG. 3 of the present invention and uses it as a sealing layer. On the substrate, the gas barrier laminate of the present invention is sequentially laminated with an organic film, an inorganic film, and an organic film. 3 is an example of a cross-sectional view in which a circuit base material is formed on a substrate 403 and further has a gas barrier property.
It shows that the periphery is sealed with a sealing layer 51 on a circuit board 902 formed on the substrate. By covering and closely adhering the light emitting element with the laminate of the present invention, it is possible to further prevent the light emitting material layer from being deteriorated by water vapor or oxygen.

  Next, the sealing agent of this invention is demonstrated. The method of adhering the sealing layer to the substrate using the sealing adhesive 700 used in FIGS. 7 and 8 may be a sealing material used in a conventionally known one, and is not particularly limited. It is preferable to use a so-called solventless adhesive that does not contain a solvent.

  Specifically, a thermoplastic resin (heat sealant) that exhibits adhesiveness by heat, a two-part adhesive composed of polyol and polyisocyanate, a pressure sensitive adhesive such as epoxy or cyanoacrylate, an acrylate oligomer, etc. And a photosensitive adhesive containing a polymerizable component. By using such a solventless adhesive, the adverse effect on the EL layer due to the solvent can be eliminated after sealing.

The substrate used in the light emitting device of the present invention has a light transmittance of 50% or more in the visible region of 400 to 700 nm, is smooth, and does not change when forming electrodes or each layer of the device. Is preferred. The average thickness of the substrate is usually 30 μm to 3 mm, preferably 50 to 300 μm.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples.
Parts and% are based on weight unless otherwise specified.

Evaluation in this example is performed by the following method.
(1) Adhesiveness When the sealing film of the laminate is cut into 100 pieces according to JIS D0202-1988 in accordance with a cross-cut cello tape test, and the tape is attached to each cut piece, and then peeled off as vertically as possible. Count the number of unpeeled pieces. The smaller the number of pieces, the better the adhesion.
(2) The water absorption was measured by measuring the weight before and after immersing the film-formed laminate in an oven at 60 ° C. for 30 minutes and then immersing it in water at 60 ° C. for 24 hours. The water absorption was calculated by ratio calculation.
(3) Water vapor transmission rate Based on JIS K7129 method B (infrared sensor method), water vapor transmission rate was measured using a water vapor transmission rate measuring device ("PERMATRAN" manufactured by MOCON) in an environment of 40 ° C and 90%. .
(4) Oxygen transmission rate Based on JIS K7129 method B (infrared sensor method), a water vapor transmission rate measuring device (manufactured by MOCON, "OXTRAN") was used in an environment of 25 ° C and 75%. .

When measuring the water vapor transmission rate and the oxygen transmission rate, a laminate in which a PET film (thickness: 100 μm) is used as a base film and a sealing film is formed thereon is used. And the water vapor transmission rate of a sealing film is computed from the following formulas (1). In addition, the water vapor transmission rate of only the base film is also measured.
Formula (1): P _o / d _o = (d _f / P _f + d _s / P _s ) ⁻¹
In the above formula _{(1), P o, P} f, respectively stack _{P s,} the sealing film, represents the water vapor transmission rate of the base _{film, d o, d f, d} s each laminate, the sealing film Represents the thickness of the substrate film. The smaller the water vapor transmission rate, the better the water vapor barrier property.
(5) Evaluation of organic EL emission lifetime The evaluation of the emission lifetime was carried out in an environment of 40 ° C. and 90% RH with the lower electrode layer 501 and the upper electrode layer 502 applied with a DC voltage of 5V. In addition, light was actually emitted as an organic EL light-emitting element, and the half-life (the time during which the luminance was reduced by half) indicating the lifetime of the light-emitting element was measured.

FIG. 1 is a circuit board according to the present invention.
The circuit board 801 was formed as a lower electrode layer 501 having a thickness of 100 nm on a resin base material 401 using a lithium indium alloy by a vacuum deposition method. Further, using a benzothiazole-based light emitting material, a 100 nm thick light emitting material layer 601 is laminated by vacuum deposition, and finally, a 100 nm upper electrode layer 502 is sequentially laminated by using vacuum deposition using indium / tin / oxide. Formed.
Example 1
FIG. 2 is a cross-sectional view of the gas barrier laminate in Example 1 of the present invention.
A cycloolefin polymer film having a thickness of 100 μm (made by Nippon Zeon Co., Ltd .: film made with ZEONOR 1620) as the resin substrate 400,
It is put in a CVD apparatus, C ₅ F ₈ (octafluoro-2-pentyne) is introduced as a monomer gas at a flow rate of 10 SCCM (0.0169 Pa · m ³ / s), a film is formed by a plasma CVD method, and an organic film 30 was laminated on the resin base material 400.

  The thickness of the obtained organic film 30 was 300 nm as a result of measurement with a stylus type film thickness measuring device “Deck Tack”.

Subsequently, an inorganic film 40 of SiO ₂ having a thickness of 300 nm was laminated on the organic film formed as described above to obtain a gas barrier substrate 200 having a sealing film 50. During film formation, the transparent film substrate 400 is not subjected to forced heating.
The evaluation results of the obtained laminate are shown in Table 1.

Example 2
FIG. 3 is a cross-sectional view of a gas barrier laminate in Example 2 of the present invention.
The transparent film substrate 400 in Example 2 was the same as that in Example 1.
A 300 nm organic film 31 was formed on the resin substrate 400 in the same manner as in Example 1. Then, an inorganic film 41 of 200 nm was formed on the organic film.
Further, by the same method as described above, a 300 nm organic film 32 and a 200 nm inorganic film 42 were sequentially laminated to obtain a gas barrier substrate 201 having a sealing film 51. The evaluation results of the obtained laminate are shown in Table 1.

Example 3
FIG. 4 is a cross-sectional view of a gas barrier laminate in Example 3 of the present invention.
A gas barrier group having a gas barrier layer 52 by laminating a 300 nm inorganic film 43 and a 200 nm organic film 33 on a resin substrate 401 in the same manner as in Example 1 and subsequently laminating a 300 nm inorganic film 44 sequentially. Material 202 was obtained. The evaluation results of the obtained laminate are shown in Table 1.

Comparative Example 1
A gas barrier laminate was prepared in the same manner as in Example 1 except that an inorganic layer was laminated without forming an organic film on a resin substrate. The evaluation results of the obtained laminate are shown in Table 1.

Comparative Example 2
Gas barrier lamination was performed in the same manner as in Example 1 except that C ₃ F ₈ (octafluoropropane) was introduced as a monomer gas instead of C ₅ F ₈ at a flow rate of 20 SCCM (0.0338 Pa · m ³ / s). Got the body. The evaluation results of the obtained laminate are shown in Table 1.

実施例で明らかなように、本発明のごとく透明樹脂基板に無機膜と有機膜の積層体、すなわち有機膜がパーフルオロカーボン分解重合物を形成されていることにより、水蒸気透過速度が低く、剥離試験においても密着性の良好な積層体を得ることができることが明白である。 In Examples 1 and 2, it is confirmed that the water vapor transmission rate (WVTR) and the oxygen transmission rate (OTR) are lower than the results of the comparative example.
From the results of Example 3, it is confirmed that the water vapor transmission rate (WVTR) and the oxygen transmission rate (OTR) are further decreased when the number of organic films and inorganic films is further increased.
It can be seen that the adhesiveness does not peel and a good result is obtained.
Moreover, it can confirm that a water absorption is 0.1 weight% or less.

As is apparent from the examples, the laminate of the inorganic film and the organic film on the transparent resin substrate as in the present invention, that is, the organic film is formed with the perfluorocarbon decomposition polymer, the water vapor transmission rate is low, and the peel test It is clear that a laminate with good adhesion can be obtained even in

FIG. 5 is a cross-sectional view of the gas barrier laminate and the light emitting device in the present invention.
A 300 nm inorganic film 45 and a 200 nm organic film 34 were stacked on the circuit board 801 in the same manner as in Example 1, and then a 300 nm inorganic film 46 was sequentially stacked to obtain a gas barrier layer 52. As a result, an organic EL light emitting device 203 sealed with the gas barrier laminate 52 was obtained.
When the organic EL light emitting device was actually made to emit light and the light emission lifetime half-life was measured, it was 3900 hours. When the organic EL element was produced with the gas barrier laminate produced in Comparative Example 2 and subjected to the same measurement, the half-life was 900 hours.

FIG. 6 is a cross-sectional view of the gas barrier laminate and the light emitting device in the present invention.
In creating a resin substrate, a cycloolefin polymer film having a thickness of 100 μm (manufactured by ZEON Corporation: film made with ZEONOR 1620) as the resin substrate 401,
In a CVD apparatus, C ₅ F ₈ (octafluoro-2-pentyne) is introduced as a monomer gas at a flow rate of 10 SCCM (0.0169 Pa · m ³ / s), a film is formed by plasma CVD, The organic film 35 was laminated on the resin base material.
Subsequently, an inorganic film 47 of SiO ₂ having a thickness of 300 nm was laminated on the organic film formed as described above to obtain a gas barrier substrate 200 having a sealing film 54.
A 300 nm inorganic film 48 and a 200 nm organic film 36 are stacked on the obtained circuit board 200 in the same manner as in the first embodiment, and then a 300 nm inorganic film 49 is sequentially stacked to have a gas barrier layer 55. A gas barrier substrate 200 was prepared.
Further, for the circuit board 802, a lower electrode layer 501 having a thickness of 100 nm was formed on the resin substrate 200 by using a lithium indium alloy by vacuum deposition. Further, a 100 nm light emitting material layer 601 is formed by vacuum evaporation using a benzothiazole-based light emitting material, and finally, an upper electrode layer 502 of 100 nm is stacked by vacuum evaporation using indium, tin, and oxide. It was.
A 300 nm inorganic film 48 and a 200 nm organic film 36 were laminated on the circuit board in the same manner as in Example 1, and then a 300 nm inorganic film 49 was sequentially laminated to obtain a gas barrier layer 55.
As a result, an organic EL light emitting device 203 sealed with the gas barrier laminate 55 was obtained. An organic EL light emitting device 202 sealed with the gas barrier laminate 55 was obtained.
An organic EL element was prepared, the lower electrode layer 501 and the upper electrode layer 502, a DC voltage of 5 V was applied to cause light emission, and the light emission lifetime half-life was measured to be 4000 hours. When an organic EL element was produced from the gas barrier laminate produced in Comparative Example 2 and subjected to the same measurement, the half-life was 1200 hours.

FIG. 7 is a cross-sectional view of the gas barrier laminate and the light emitting device in the present invention.
The organic EL element 901 is formed on the circuit board 401 by covering the circuit board with the gas barrier laminate 51 created in Example 1 and sealing with the epoxy adhesive 700.
The evaluation of the light emission lifetime was 4000 hours when the lower electrode layer 501 and the upper electrode layer 502 were applied with a DC voltage of 5 V to emit light and the light emission lifetime half-life was measured.
When the same measurement was performed on the gas barrier laminate produced in Comparative Example 2, the half-life was 1100 hours.

FIG. 8 is a cross-sectional view of the gas barrier laminate and the light emitting device in the present invention.
In creating a resin substrate, a cycloolefin polymer film having a thickness of 100 μm (manufactured by ZEON Corporation: film made with ZEONOR 1620) as the resin substrate 401,
In a CVD apparatus, C ₅ F ₈ (octafluoro-2-pentyne) is introduced as a monomer gas at a flow rate of 10 SCCM (0.0169 Pa · m ³ / s), a film is formed by plasma CVD, The organic film 35 was laminated on the resin base material.
Subsequently, an inorganic film 47 of SiO ₂ having a thickness of 300 nm was laminated on the organic film formed as described above to obtain a gas barrier substrate 200 having a sealing film 54.
This is an organic EL element 901 created by sealing the circuit board with the epoxy adhesive 700 on the circuit board 403 with the gas barrier laminate 51 produced in Example 3.
The evaluation of the light emission lifetime was 4200 hours when the lower electrode layer 501 and the upper electrode layer 502 and a DC voltage of 5 V were applied to emit light and the half-life was measured.

Therefore, it is very useful as a substrate for a display device such as a liquid crystal display device or an organic EL device that requires thinness, lightness, and flexibility; a sealant for the display device;
Furthermore, the processing time can be shortened, and the productivity can be improved.

It is sectional drawing which shows the structure of a typical organic EL element. An example sectional view using a gas barrier layered product of the present invention is shown. An example sectional view using a gas barrier layered product of the present invention is shown. An example sectional view using a gas barrier layered product of the present invention is shown. It is sectional drawing which shows an example which used the gas barrier laminated body of this invention for the sealing layer on the resin base material which has a light-emitting body. It is sectional drawing which shows an example which used the gas barrier laminated body of this invention for the sealing layer on the resin base material which has a light-emitting body. It is sectional drawing which shows an example sealed on the resin base material which has a light-emitting body using the gas barrier laminated body of this invention as a sealing layer, and with the sealing agent. The gas barrier laminate of the present invention was laminated on a resin substrate having a light emitter, and the gas barrier laminate of the present invention was used as a sealing layer and sealed with a sealant to produce an organic EL light emitting device. It is sectional drawing which shows an example.

Explanation of symbols

400: Resin film substrate 401: Resin film substrate 200: An example of a laminate in which an organic film and an inorganic film are laminated on a resin film substrate 201: A laminate in which a plurality of organic films and inorganic films are sequentially laminated on a resin film substrate An example of a body 403: An example of a laminate in which an organic film, an inorganic film, and an organic film are laminated on a resin film base material 901: Organic EL light emitting elements 801, 902: Circuit boards 30, 31, 32, 33 of the organic EL light emitting elements , 34, 35, 36: organic films 40, 41, 42, 43, 44, 45, 46, 47, 48, 49: inorganic film 50: an example of a laminate in which an organic film and an inorganic film are laminated 51: organic film An example 53 of a laminate in which a plurality of inorganic films are laminated 53: An example of a laminate in which an organic film and an inorganic film are sequentially laminated on a resin film substrate 54: An example of an organic film and an inorganic film laminate 55 laminated on a resin film substrate 55 : Organic An example of an inorganic film laminate 200: An example of a laminate in which an organic film and an inorganic film laminate are laminated on a resin film substrate 201: A laminate in which a plurality of organic films and inorganic film laminates are sequentially laminated on a resin film substrate Example 403: Example of laminate in which a plurality of organic films and inorganic film laminates are sequentially laminated on a resin film substrate 902: Circuit board 52 in which a plurality of organic films and inorganic film laminates are sequentially laminated on a resin film substrate : An example of an organic film or inorganic film laminate laminated on a resin film substrate 202: An example of a laminate laminated on a resin film substrate 203: A cross-sectional view of an organic EL light emitting device 501: A lower electrode layer 502: An upper electrode Layer 601: Light emitting material layer 700: Sealing material for laminated body

Claims (7)

A laminate comprising a sealing film formed by laminating at least one organic film and at least one inorganic film, and a transparent resin film substrate, wherein the organic film is formed of a perfluoroolefin decomposition polymer. A gas barrier laminate characterized by that. The gas barrier laminate according to claim 1, wherein the organic film is formed by introducing perfluoroolefin in a gaseous state under vacuum. The gas barrier laminate according to claim 1 or 2, wherein the inorganic film is a metal or metalloid compound formed under vacuum. The gas barrier laminate according to any one of claims 1 to 3, wherein the water absorption of the organic film is 0.1 wt% or less. The gas barrier laminate according to claim 1, wherein the light transmittance at a wavelength of 550 nm is 70% or more. A sealing film in which at least one organic film and at least one inorganic film are laminated on a circuit board in which a lower electrode layer, a light emitting material layer, and an upper electrode layer are sequentially laminated on at least one of the substrates. A light emitting device, wherein the organic film forms a perfluoroolefin decomposition polymer. The light emitting element formed by sealing the circuit board which formed the lower electrode layer, the luminescent material layer, and the upper electrode layer in order on at least one of the board | substrates with the gas barrier laminated body of Claim 1.

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