JP2005335067A - 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 at the interface with an inorganic film or the flaw accompanied by peeling, having high adhesion and extremely low in degassing. <P>SOLUTION: The gas barrier laminate is constituted by forming the inorganic film and the organic film on one side or both sides of a transparent resin film base material, and the polymer molecule of the surface layer part of the base material contains a fluorine atom and the fluorine compound polymer film containing an element or a metal compound is used as the organic film. <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 resin film substrate has been used as a packaging material for foods and drugs. 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. This resin film base material is required to have a higher gas barrier property, particularly a water vapor barrier property than conventional packaging materials.

Conventionally, single-layer films of inorganic oxides such as silicon dioxide (SiO ₂ ) and aluminum oxide (Al ₂ O ₃ ) have been mainly used as gas barrier layers. However, when the film thickness is small, 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, so that the film is likely to crack, and the gas barrier property decreases due to the crack. 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 (Patent Document 1, Patent Document 2, Patent Document 3, and Patent Document 4). According to this report, by laminating an organic film and an inorganic film, the organic film has gas barrier properties, 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. The inventors have found that this water vapor prevents the formation of a high-density inorganic film on the resin. Theoretically, in order to achieve high gas barrier properties, 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 (Patent Document 5). However, the fluorine compound polymer has extremely low adhesion to the inorganic film.

  The present applicant has also 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 (Patent Document 6). ). 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 inventors of the present invention have achieved a sealing film comprising a laminate in which an inorganic film and an organic film are laminated on a transparent resin film substrate, and the surface layer of the transparent resin film substrate. Part of the polymer molecule contains fluorine atoms,
The organic film is a film made of a fluorine compound, or a fluorine compound and a simple substance of a metal or a compound as a raw material,
The present inventors have found that the above object can be achieved by forming a gas barrier laminate in which the inorganic film is a film made of a single metal or a compound as a raw material, and the present invention has been completed.

Thus, according to the present invention,
(1) 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,
The polymer molecule in the surface layer part of the transparent resin film substrate contains a fluorine atom,
The organic film is a film made of a fluorine compound, or a raw material of a fluorine compound and a metal or metalloid simple substance or compound,
A gas barrier laminate in which the inorganic film is a film made of a single metal or a compound as a raw material.
(2) The said gas barrier laminated body whose volume composition ratio F / M of the fluorine atom F and the metal atom M which are contained in the said organic film is 0.01-0.99.
(3) The gas barrier laminate according to (1) or (2), wherein the organic film is formed by a chemical vapor deposition method.
(4) The gas barrier laminate according to any one of (1) to (3), wherein the water absorption of the organic film is 0.1% by weight or less.
(5) The gas barrier laminate according to any one of (1) to (4), wherein the inorganic film is a metal or metalloid compound formed under vacuum.
(6) A lower electrode layer, a light emitting material layer, an upper electrode layer, and a sealing layer are sequentially stacked on a substrate, and the sealing layer is the gas barrier laminate according to any one of (1) to (5). Light emitting element.
(7) A light emitting device in which a lower electrode layer, a light emitting material layer, an upper electrode layer, and a sealing layer are sequentially laminated on a substrate, and the substrate is the gas barrier laminate according to any one of (1) to (5). .
(8) A light emitting device in which a lower electrode layer, a light emitting material layer, and an upper electrode layer are sequentially laminated on a substrate, and further, at least one organic film and at least one inorganic film are laminated thereon,
The polymer molecule in the surface layer portion of the transparent resin film substrate contains a fluorine atom,
The organic film is a film made of a fluorine compound, or a raw material of a fluorine compound and a metal or metalloid simple substance or compound,
A light-emitting element in which the inorganic film is a film made of a single metal or a compound as a raw material.
(9) A lower electrode layer, a light emitting material layer, an upper electrode layer, and a sealing layer are sequentially stacked on a substrate, and the substrate and the sealing layer are stacked in the gas barrier according to any one of (1) to (5). A light-emitting element consisting of a body.
(10) A lower electrode layer, a light emitting material layer, an upper electrode layer, and a sealing layer are sequentially laminated on a substrate, and the substrate is the gas barrier laminate according to any one of (1) to (5),
The sealing layer is formed by laminating a sealing film formed by laminating at least one organic film and at least one inorganic film,
The organic film is a film made of a fluorine compound, or a fluorine compound and a metal or metalloid simple substance or compound as a raw material,
A light-emitting element in which the inorganic film is a film made of a single metal or a compound as a raw material.
(11) The light emitting device according to any one of (6) to (10), wherein the light transmittance at a wavelength of 550 nm when not emitting light is 80% or more.

The gas barrier laminate of the present invention is a laminate film that is excellent in adhesion between a substrate, an organic film and an inorganic film, and further has a stronger film and is excellent in water vapor barrier properties and gas barrier properties.
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,
The organic film is a film made of a fluorine compound, or a fluorine compound and a metal simple substance or compound, the inorganic film is a film made of a metal simple substance or compound, and the transparent resin film substrate The polymer molecule in the surface layer part contains a fluorine atom.

  The gas barrier laminate of the present invention is obtained 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 transparent resin film substrate may be an organic film or an inorganic film, but when the organic film is in contact with the transparent resin film substrate, there are irregularities on the surface of the transparent resin film substrate. However, since the surface is smoothed by forming the organic film thereon, the inorganic film formed thereon is preferable because it is a dense and smooth film without defects and has high gas barrier properties.

 Further, in this embodiment, even if the transparent resin film substrate receives an external force, it is relaxed by the organic film, so that the inorganic film is hardly cracked, and high gas barrier properties are maintained for a long time.

Regarding the organic film, the fluorine compound which is a constituent material of the organic film is an organic compound containing a fluorine atom in the molecular structure. The structures of these compounds include chain and ring. Moreover, the said fluorine compound may contain a small amount of the inorganic compound which contains a fluorine atom in molecular structure.
The fluorine compound preferably has 1 to 8 carbon atoms, more preferably 1 to 7 carbon atoms.

  Of these, unsaturated fluorocarbon compounds and unsaturated fluorinated hydrocarbon compounds are preferred, and unsaturated fluorocarbon compounds are more preferred from the viewpoint of easy polymerization and high film formation rate.

As a specific example of a saturated fluorine compound,
Trifluoromethane, difluoromethane, trifluoroethane, tetrafluoroethane, pentafluoropropane, hexafluoropropane, heptafluoropropane; hexafluorocyclopropane, octafluorocyclobutane, decafluorocyclopentane, difluoroethylene, trifluoroethylene, difluoropropene, Trifluoropropene, tetrafluoropropene, pentafluoropropene, hexafluoropropene, hexafluorobutene, octafluorobutene; difluorocyclopropene, trifluorocyclopropene, difluorocyclobutene, trifluorocyclobutene, tetrafluorocyclobutene, pentafluorocyclo Fluorinated hydrocarbon compounds such as butene;

As a specific example of the perfluoroolefin compound,
Perfluoroolefin compounds having 2 carbon atoms such as tetrafluoroethylene; perfluoroolefin compounds having 3 carbon atoms such as hexafluoropropene, tetrafluoropropyne and tetrafluorocyclopropene; hexafluoro-2-butyne and hexafluoro -1-butyne, hexafluorocyclobutene, hexafluoro-1,3-butadiene, hexafluoro- (1-methylcyclopropene), octafluoro-1-butene, octafluoro-2-butene, etc. having 4 carbon atoms Perfluoroolefin compounds; octafluoro-1-pentyne, octafluoro-2-pentyne, octafluoro-1,3-pentadiene, octafluoro-1,4-pentadiene, octafluorocyclopentene, octafluoroisoprene, hexafluorovinylacetylene, Oh Tafuruoro - (1-methyl-cyclobutene), octafluoro - (1,2-dimethyl cyclopropene) carbon atoms, such as perfluoro olefin compound 5;

Dodecafluoro-1-hexene, dodecafluoro-2-hexene, dodecafluoro-3-hexene, decafluoro-1,3-hexadiene, decafluoro-1,4-hexadiene, decafluoro-1,5-hexadiene, decafluoro -2, 4-hexadiene, decafluorocyclohexene, hexafluorobenzene, octafluoro-2-hexyne, octafluoro-3-hexyne, octafluorocyclo-1, 3-hexadiene, octafluorocyclo-1, 4-hexadiene, etc. A perfluoroolefin compound having 6 carbon atoms;
And perfluoroolefin compounds having 7 carbon atoms, such as undecafluoro-1-heptene, undecafluoro-2-heptene, undecafluoro-3-heptene, and dodecafluorocycloheptene.

  In particular, 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 More preferred are-(1-methylcyclobutene) and octafluoro- (1,2-dimethylcyclopropene).

  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.

  The organic film is preferably made of a metal or a semimetal alone or a compound together with the fluorine compound. A simple substance or compound of a metal or a semimetal which is a preferable constituent material of the organic film is a simple substance of a metal of Groups 4 to 16 of the periodic table, or an organic compound, oxide, nitride, oxynitride or halide of the metal. Etc. Among these, a group 4 metal, a group 13 metal, a group 14 metal simple substance or the above-mentioned compounds, particularly an organic compound containing aluminum or silicon is preferable.

Examples of the organic compound of aluminum include tri (isopropoxide) aluminum, tri (ethoxy) aluminum, aluminum butoxide, aluminum phenoxide, aluminum acetylacetonate, aluminum ethylacetoacetate, aluminum methacrylate, aluminum pentanedionate, etc. And complex compounds.
The amount of the aluminum-containing compound used is preferably 20% by weight or less, more preferably 10% by weight or less based on the entire fluorine compound.

Examples of silicon organic 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.

  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.

 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 raw material metal or metalloid simple substance or compound and the fluorine compound are introduced into the chamber after evacuating the pressure in the chamber of the CVD apparatus to 0.1 Pa or less.

  When the raw material is solid, it is introduced into the chamber by heating, evaporating using an electron beam, or applying high voltage to cause sputtering. When the raw material is liquid, it is evaporated using a vapor pressure difference, or the container containing the raw material is heated and evaporated with a mantle heater or the like and introduced into the chamber. When the raw material is a gas, it is introduced into the chamber as it is.

After introducing the raw material into the chamber, a direct current or alternating current (10 kHz to 100 MHz) voltage is applied at an output of about 10 W to about 10 kW to generate plasma between the electrodes, thereby forming an organic film on a predetermined substrate. The substrate temperature at that time is 500 ° C. or less, and when the transparent substrate is a resin having low heat resistance, it is preferable not to heat. The pressure in the system during film formation is preferably 1 × 10 ⁻² to 1 × 10 ⁴ Pa.

  The volume composition ratio F / M between the fluorine atom F and the metal atom M in the organic film is preferably 0.01 to 0.99, and more preferably 0.03 to 0.9. If this ratio is too small, the organic film may exhibit water absorbency, resulting in insufficient water repellency and consequently gas barrier properties. Conversely, if this ratio is too large, adhesion to the inorganic film is insufficient. There is a possibility. The measuring method of F / M is based on X-ray electron spectroscopic analysis.

  The water absorption rate of the organic film is preferably 0.1% by weight or less, and more preferably 0.05% by weight or less. When this condition is satisfied, there is little degassing (mainly water vapor generation) from the organic film, and an inorganic film formed thereon can be densely formed.

 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 vacuum vapor deposition, sputtering, and CVD are preferred from the viewpoint that a film made of an inorganic compound having a high film density can be efficiently formed. A vacuum vapor deposition method or a CVD method using arc discharge plasma is particularly preferable in that there is no damage to the material 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, and the polymer molecules in the surface layer portion contain fluorine atoms.
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 surface layer portion of the transparent resin film substrate is a portion from the outermost surface of the sheet to a depth of about several nm to several μm. Both the inner layer portion and the surface layer portion of the transparent resin film are made of the same material, and there is no laminated interface, and the polymer molecules in the surface layer portion have a higher fluorine atom content than the polymer molecules in the inner layer portion.

The fluorine atom content can be confirmed by an analyzer such as X-ray electron spectroscopy (ESCA).
The fluorine atom content may be distributed so that it gradually decreases from the polymer molecule in the surface layer portion toward the polymer molecule in the inner layer portion, or the content of fluorine atoms in the inner layer portion from the polymer molecule in the surface layer portion. The distribution may decrease stepwise toward the coalesced molecule.

The method for obtaining the transparent resin film substrate of the present invention will be described more specifically with reference to the drawings.
The transparent resin film substrate can be obtained by a solution casting method or a melt extrusion method. Among these, the melt extrusion molding method is preferable because the content of volatile components in the transparent 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 method of forming a layer containing fluorine atoms on the polymer molecules of the surface layer of the transparent resin film substrate includes bringing the transparent resin film substrate obtained by the above production method into contact with an atmosphere containing fluorine gas. It is a waste.

FIG. 8 shows an example of a reaction apparatus used for obtaining the present invention. This reaction apparatus includes a chamber 1 and a heating device 5 for controlling the temperature of the chamber, and a fluorine gas supply line 2 and an inert gas supply line 3 for introducing fluorine gas and inert gas into the chamber. Are connected.
An exhaust line 4 for extracting unnecessary gas is connected to another position of the chamber. The chamber has a space where the transparent resin film substrate 6 can be placed, and the transparent resin film substrate 6 can be placed there. The gas extracted from the exhaust line 4 can be recycled as it is or can be separated and purified and returned to each gas supply line.

The fluorination according to the present invention will be described step by step.
(1) A step of leaving the transparent resin film substrate in an inert gas atmosphere or under reduced pressure.
This step (1) is not necessarily a step that must be performed, but by passing through this step, a layer of a material having a high fluorine atom content can be present in the surface layer of the transparent resin film substrate without in-plane distribution. Since it becomes possible, it is preferable to go through step (1).
In the step (1), first, the transparent resin film substrate is placed in the chamber, the chamber is closed, the valve of the inert gas supply line 3 is opened, and the inert gas flows into the chamber. Examples of the inert gas include argon, nitrogen, helium, neon, krypton, and xenon.

In the present invention, argon is preferably used. The chamber used is preferably made of stainless steel or aluminum.
It is preferable that the transparent resin film substrate in the chamber is heated with a heating device in an inert gas atmosphere. By this heating, moisture, oxygen, and volatile components contained in the transparent resin film substrate can be efficiently removed. The heating temperature is the surface temperature of the transparent resin film substrate, and is usually 60 to 180 ° C, preferably 80 to 130 ° C. The heating time is 1 to 360 minutes, preferably 2 to 200 minutes.

Instead of leaving in an inert gas atmosphere, the transparent resin film substrate may be left under reduced pressure.
When left under reduced pressure, the pressure is usually 500 mmHg or less, preferably 100 mmHg or less.
The lower limit of the pressure is 1 mmHg. If the pressure is extremely reduced, contaminants such as oil and moisture may reversely diffuse from the exhaust system. Heating is also preferred when left under reduced pressure. The heating temperature is usually 15 to 100 ° C. In addition, it is preferable to inject a high-purity inert gas simultaneously with decompression because the amount of oxygen and water can be efficiently removed. The decompression time is 1 to 360 minutes, preferably 1 to 200 minutes.

  If oxygen or moisture is present in the transparent resin film substrate in the next step (2), the surface is easily hydrophilized, and therefore it is preferable to reduce the amount of oxygen or moisture in step (1). The amount of oxygen and water in the preferred transparent resin film substrate is usually 1% by weight or less, preferably 100 ppm by weight or less, more preferably 10 ppm by weight or less.

(2) A step of bringing the transparent resin film substrate into contact with an atmosphere containing fluorine gas.
After step (1), the valve of the inert gas supply line is closed, the chamber is cooled if necessary, and then the valve of the fluorine gas supply line 2 and the valve of the inert gas supply line 3 are opened if necessary, Fluorine gas is allowed to flow into the chamber, and the chamber is brought into an atmosphere containing fluorine gas.
The atmosphere containing fluorine gas may be an atmosphere composed only of fluorine gas, but is preferably composed of fluorine gas diluted with an inert gas in order to moderate the reaction. The atmosphere containing fluorine gas is preferably free of oxygen and water. Specifically, the amount of oxygen and water is preferably 100 ppm by weight or less, more preferably 10 ppm by weight or less, and particularly preferably 1 ppm by weight or less.

  By bringing the surface of the transparent resin film base material into contact with an atmosphere containing fluorine gas, the fluorine gas gradually moves from the surface of the transparent resin film base material to the surface layer part, and further toward the inner layer part. The introduction occurs, and the fluorine atom content in the material constituting the transparent resin film substrate increases. The penetration depth of fluorine atoms from the surface of the transparent resin film substrate and the content of fluorine atoms vary depending on the concentration, temperature, and time of the fluorine gas.

  The concentration of the fluorine gas diluted with an inert gas is usually 0.1 to 50% by volume, preferably 0.1 to 30% by volume, more preferably 0.1 to 20% by volume. The surface temperature of the transparent resin film substrate when contacting with the fluorine gas is not particularly limited, but is usually −50 to 150 ° C., preferably −20 to 80 ° C., and particularly preferably 0 to 50 ° C. The contact time is usually 0.1 second to 600 minutes, preferably 0.5 seconds to 300 minutes, more preferably 1 second to 60 minutes.

  When the fluorine gas concentration is high, the temperature is high, or the time is long, the penetration depth of fluorine atoms becomes deep and the fluorine atom content increases. When the fluorine gas concentration is extremely high, or when the temperature is extremely high for a long time, the material constituting the transparent resin film substrate deteriorates. Therefore, it is preferable to contact the fluorine gas within the above range.

(3) A step of leaving the transparent resin film substrate subjected to the fluorine gas contact treatment in an inert gas atmosphere or under reduced pressure after leaving the fluorine gas in contact.
After contacting a fluorine gas and a predetermined time has elapsed, the inert gas supply line 3 is opened, the valve of the fluorine gas supply line 2 is closed, and the chamber is brought to an inert gas atmosphere. Examples of the inert gas include the same as described in the step (1). And it is preferable to heat a transparent resin film base material with a heating apparatus. Excessive fluorine gas that could not be introduced into the transparent resin film substrate by this heating can be removed. The heating temperature is the surface temperature of the transparent resin film substrate, and is usually 60 to 180 ° C, preferably 80 to 130 ° C. The heating time is 1 to 120 minutes, preferably 2 to 90 minutes.

 Instead of leaving in an inert gas atmosphere, a transparent resin film substrate subjected to a fluorine gas contact treatment under reduced pressure may be left. When left under reduced pressure, the pressure is usually 500 mmHg or less, preferably 100 mmHg or less. The lower limit of the pressure is 1 mmHg. If the pressure is extremely reduced, contaminants such as oil and moisture may reversely diffuse from the exhaust system. Heating is also preferred when left under reduced pressure. The heating temperature is usually 15 to 100 ° C. In addition, it is preferable to inject a high-purity inert gas simultaneously with the decompression because the fluorine gas can be efficiently removed. The decompression time is 1 to 120 minutes, preferably 1 to 60 minutes.

This step (3) is not necessarily a step, but by passing through this step, the phase of the material having a high fluorine atom content can be present in the surface layer of the transparent resin film substrate without in-plane distribution. Since it becomes possible, it is preferable to go through step (3).
After the step (3) is completed, the transparent resin film substrate can be taken out of the chamber and used according to each application.

  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 causing deformation or stress in 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 within 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 is likely to be peeled off during long-term use. Furthermore, there is a possibility that productivity and yield may be lowered 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.

As the transparent resin base material, one having one or both surfaces subjected to surface modification treatment may be used. By performing the surface modification treatment, the adhesion with an organic film or an inorganic film can be improved. Examples of the surface modification treatment include energy beam irradiation treatment and chemical treatment.
Examples of the energy beam irradiation treatment include corona discharge treatment, plasma treatment, electron beam irradiation treatment, ultraviolet ray irradiation treatment, and the like. From the viewpoint of treatment efficiency, corona discharge treatment and plasma treatment, particularly corona discharge treatment is preferable.

  As the transparency of the transparent resin film substrate used in the present invention, the total light transmittance based on ASTM D1003 is preferably 70% or more, more preferably 80% or more. If the total light transmittance is too small, it may be difficult to use for transparent purposes.

In the gas barrier laminate of the present invention, an organic film and an inorganic film are laminated on a transparent resin film substrate containing fluorine atoms in the surface layer portion of the transparent resin film substrate.
Therefore, the adhesion at each interface is high, and the gas barrier property, particularly the water vapor barrier property, is remarkably high. Furthermore, since any of the transparent 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 circuit board as a basic element constituting a typical organic EL light emitting device.
A circuit board 801 shown in FIG. 1 is formed by sequentially laminating a substrate 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 or oxygen, and in order to extend the life of the organic EL light emitting element, it is indispensable to seal the light emitting material layer 601 with a gas barrier film and prevent water vapor and oxygen from entering.

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. Further, 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 for the upper electrode layer to be transparent or translucent to transmit light emission or to improve the light extraction efficiency. 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 501 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.

In addition to the above layers, the circuit board that is a basic element of the light-emitting element may have other layers.
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 has 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 is 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 driving voltage and the light emission efficiency are appropriate 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, has a function of improving electron injection efficiency from the upper electrode, and has an effect of lowering 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 have a transparent resin film substrate 400 in which the polymer molecules in the surface layer portion of the transparent resin film substrate contain fluorine atoms (hereinafter referred to as fluorinated), an organic film, And a sealing film formed by sequentially laminating inorganic films. The organic film and the inorganic film were laminated using the plasma CVD method.
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 light emitting device of the present invention, it is preferable that a sealing layer comprising the laminate of the present invention 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 further the transparent resin film substrate can be covered. Further preferred.
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 in addition to the dry manufacturing method, a pressure bonding method, a thermocompression bonding method, an adhesive method, or the like can be used as long as it is sealed by close contact.

FIG. 5 is a diagram showing an example of the light emitting device of the present invention.
In the embodiment of the light emitting element of the present invention, a fluorinated substrate 403, a lower electrode layer 501, a light emitting material layer 601, an upper electrode layer 502, and a sealing layer 53 are sequentially laminated.
The fluorinated substrate 403 was obtained by bringing the transparent resin film base material into contact with fluorine gas.
The organic film of the sealing layer 53 and the lamination method of the inorganic film were laminated | stacked so that a circuit board might be covered using the above-mentioned plasma CVD method.

6 uses the gas barrier laminate 200 laminated in the configuration of FIG. 2 as a substrate, and sequentially laminates a lower electrode layer 501, a light emitting material layer 601, an upper electrode layer 502, and a sealing layer 55 on the substrate 200. It is an example of sectional drawing which gave nature further.
In the embodiment of the light emitting device of the present invention, a substrate 200 made of a gas barrier laminate, a lower electrode layer 501, a light emitting material layer 601, an upper electrode layer 502, and a sealing layer 55 are sequentially laminated.
As a method of laminating the organic film and the inorganic film of the sealing layer 55, the circuit substrate was laminated using the plasma CVD method described above.
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 circuit board is covered with the gas barrier laminate 201 laminated in the configuration of FIG. 3 of the present invention and used as a sealing layer.
The embodiment of the light-emitting element of the present invention has a structure in which the periphery is sealed with a sealing layer 201 on a circuit board 801, and an example in which the sealing layer 201 is sealed with an adhesive 700 is shown.
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.

FIG. 8 shows the use of a gas barrier laminate in which an organic film 36, an inorganic film 48, and an organic film 37 are sequentially laminated on a fluorinated substrate 404 as a substrate 403.
A circuit substrate is formed by laminating a lower electrode layer 501, a light emitting material layer 601 and an upper electrode layer 502 on a substrate 403,
3 is an example of a cross-sectional view in which a circuit board is covered with a gas barrier laminate 201 laminated in the same manner as described in FIG. 3 of the present invention, used as a sealing layer, and further provided with gas barrier properties.
By covering and closely contacting the circuit board with the laminate of the present invention, it is possible to further prevent the light emitting material layer from being deteriorated due to 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 adhesive 700 for sealing 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 in the visible region of 550 nm of 80% or more, is smooth, and does not change when forming electrodes or each layer of the device. preferable. 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) Adhesion According to JIS D0202-1988, the cross-cut cellophane tape test is used to cut the sealing film of the laminate into 100 pieces, and a cellophane tape is applied to each cut piece, and then peeled off as quickly and vertically as possible. It was. The number of pieces of the sealing film not peeled off is counted. The smaller the number of pieces, the better the adhesion.
(2) The water absorption was dried in an oven at 60 ° C. for 30 minutes. Thereafter, the laminate was immersed in water at 60 ° C. for 24 hours, and the weight before and after immersion was measured. 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%. .
(5) Volume composition ratio (F / M) of fluorine atoms and metal atoms in the organic film
The organic film sample was measured with an X-ray electron spectrometer, and the volume composition ratio (F / M) of the organic film was calculated.

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.
(6) Evaluation of organic EL light emission lifetime The evaluation of the light emission lifetime was carried out in an environment of 40 ° C. and 90% RH with a DC voltage applied to the lower electrode layer 501 and the upper electrode layer 502. Continuous driving was performed under the condition that the initial light emission luminance was 100 cd / m ² , light was emitted as the organic EL light emitting device, and the half-life indicating the lifetime of the light emitting device (the time when the luminance was reduced by half) was measured. The longer the time, the better the light emission life.

FIG. 1 is a diagram showing a circuit board used in this embodiment.
The circuit board 801 was formed on the transparent resin film base 401 as a lower electrode layer 501 having a thickness of 100 nm by a vacuum vapor deposition method using a lithium indium alloy. 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 100 μm-thick cycloolefin polymer film (manufactured by ZEON Corporation: film made with ZEONOR 1620) as a transparent resin film substrate 400 is placed in a SUS316L chamber, and a high-purity argon stream having an oxygen and moisture content of 1 weight ppb or less. Under heating at 120 ° C. for 3 hours, oxygen and water were removed. The amount of oxygen and water was less than 10 ppm by weight.
Then, cool to room temperature, switch the valve while taking care not to mix oxygen and moisture from the outside air, diluted with argon gas 1% by volume fluorine gas (oxygen and water content less than 1 ppm by weight) Was introduced at 30 ° C. After 15 minutes, the valve was switched to introduce high-purity argon having an oxygen and water content of 1 weight ppb or less, and the mixture was heated at 90 ° C. for 1 hour to remove excess fluorine gas.

It was confirmed by ESCA measurement that many fluorine atoms exist in the surface layer portion of the transfer surface. Furthermore, when this transparent resin film base material was immersed in ultrapure water for 24 hours and then measured for ESCA, many fluorine atoms were present in the surface layer portion as before the immersion. Further, when the film surface was measured by the FTIR-ATR method, a broad peak was observed at 1400 to 1000 cm ⁻¹ derived from C—F stretching vibration.

The transparent resin film substrate subjected to the fluorination treatment is put in a CVD apparatus, and the flow rates of C ₅ F ₈ (octafluoro-2-pentyne) and tetraethoxysilane (TEOS) as monomer gases are set to 0.101 Pa · m ³ / Introduced at sec and 0.0676101 Pa · m ³ / sec (volume flow rate ratio 60:40), a film was formed by a plasma CVD method, and the organic film 30 was laminated on the fluorinated transparent resin film substrate 400.

  The thickness of the obtained organic film 30 was 250 nm as a result of measurement with a stylus type film thickness measuring device “Deck Tack”.

Subsequently, a 200 nm-thick SiO ₂ inorganic film 40 was laminated on the organic film formed as described above by the same method as described above.
As a result, a gas barrier laminate 200 having the sealing film 50 was obtained. During film formation, the fluorinated 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 same fluorinated transparent resin film substrate 400 as in Example 2 was used as in Example 1.
A 250 nm organic film 31 was formed on the fluorinated resin film 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 gas barrier laminate 201 having a sealing film 51 was obtained by sequentially laminating an organic film 32 of 250 nm and an inorganic film 42 of 200 nm. 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.
In the same manner as in Example 1, the 300 nm inorganic film 43 and the 200 nm organic film 33 were laminated on the fluorinated transparent resin film substrate 400 in the same manner as in Example 1, followed by 200 nm. Inorganic films 44 were sequentially laminated to obtain a gas barrier laminate 202 having a gas barrier layer 52.
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 a transparent resin film substrate not subjected to fluorination treatment was used. The evaluation results of the obtained laminate are shown in Table 1.

Comparative Example 2
A gas barrier laminate was prepared in the same manner as in Example 2 except that a transparent resin film substrate not subjected to fluorination treatment was used. 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フィルム基材の表層部の重合体分子がフッ素原子を含有した透明樹脂フィルム基材をもちい、該基材上に無機膜と有機膜の積層体を形成することにより、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 clear from the examples, a transparent resin film base material in which the polymer molecules in the surface layer portion of the transparent resin film base material contain fluorine atoms as in the present invention is used, and an inorganic film and an organic film are laminated on the base material. By forming the body, it is apparent that a laminate having a low water vapor transmission rate and good adhesion can be obtained even in a peel test.

Example 4
FIG. 5 is a cross-sectional view of the light emitting device of the present invention.
Using the substrate 403 obtained by fluorinating the surface layer portion of the 100 μm-thick cycloolefin polymer film base material in the same manner as in Example 1, on the circuit board 802 created by the same method described in FIG.
In the same manner as in Example 1, a 300 nm inorganic film 45 and a 250 nm organic film 34 were stacked, and then a 300 nm inorganic film 46 was sequentially stacked to obtain a gas barrier layer 53. As a result, an organic EL light emitting device 203 sealed with the gas barrier laminate 53 was obtained.
It was 4500 hours when the organic EL light emission lifetime evaluation of this organic EL light emitting element was implemented and the light emission lifetime half life was measured.
Comparative Example 3
A circuit board and a light emitting device were prepared in the same manner as in Example 4 except that a cycloolefin polymer film substrate having a thickness of 100 μm was used as a substrate without being fluorinated, and an organic EL light emitting lifetime evaluation was performed. The half life was 3900 hours.

Example 5
FIG. 6 is a cross-sectional view of the light emitting device of the present invention.
A 100 μm-thick cycloolefin polymer film (made by Nippon Zeon Co., Ltd .: ZEONOR 1620) as a transparent resin film substrate 403 is subjected to fluorination treatment by the method of Example 1, and polymer molecules in the surface layer portion of the film The one containing fluorine atoms was used.
The substrate was put in a CVD apparatus, and the flow rates of C ₅ F ₈ (octafluoro-2-pentyne) and tetraethoxysilane (TEOS) as monomer gases were set to 0.101 Pa · m ³ / sec and 0.0676101 Pa · m ^3. / Sec (volume flow rate ratio 60:40), a film was formed by plasma CVD, and a 250 nm organic film 35 was laminated on the resin substrate.
Subsequently, a 300 nm-thick SiO ₂ inorganic film 47 was laminated on the formed organic film in the same manner as in Example 1 to obtain a gas barrier substrate 200 having a sealing film 54.
Further, as the circuit board 803, a lower electrode layer 501 having a thickness of 100 nm was formed on the gas barrier board 200 using a lithium indium alloy by vacuum deposition. Furthermore, 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 formed by sequentially depositing indium, tin, and oxide using vacuum evaporation. It was.
On the obtained circuit board 803, a 300 nm inorganic film 48 and a 250 nm organic film 36 are laminated in the same manner as in Example 1, and then a 300 nm inorganic film 49 is sequentially laminated to have a gas barrier layer 55. A light emitting element 204 was prepared.
When a direct current voltage was applied to the lower electrode layer 501 and the upper electrode layer 502 of the produced light emitting element, an organic EL light emission lifetime was evaluated, and a light emission lifetime half-life was measured, it was 4800 hours.
Comparative Example 4
Using the gas barrier laminate produced in Comparative Example 2 as a substrate, a circuit board and a gas barrier layer were produced in the same manner as described above to obtain a light emitting device. When the organic EL light emission lifetime was evaluated, the half-life was 4000 hours.

Example 6
FIG. 7 is a cross-sectional view of the gas barrier laminate and the light emitting device in the present invention.
The circuit board 801 created by the same method described with reference to FIG. 1 is covered with the gas barrier laminate 201 created in Example 1 and sealed with the epoxy adhesive 700, and the produced organic EL light emitting device 901 is formed. It is.
When a direct current voltage was applied to the lower electrode layer 501 and the upper electrode layer 502 of the produced light emitting element, an organic EL light emission lifetime was evaluated, and a light emission lifetime half-life was measured, it was 4300 hours.
Comparative Example 5
A light emitting device was produced in the same manner as in Example 6 except that the circuit board was covered with the gas barrier laminate produced in Comparative Example 2. When the luminescence lifetime half-life was measured, the half-life was 4000 hours.

Example 7
FIG. 8 is a cross-sectional view of the light emitting element.
In preparing a transparent resin film substrate, a cycloolefin polymer film having a thickness of 100 μm (manufactured by Nippon Zeon Co., Ltd .: ZEONOR 1620) as a substrate 404 was fluorinated by the method of Example 1, and the substrate Fluorine atoms were contained in the polymer molecules in the surface layer portion.
The substrate was put in a CVD apparatus, and the flow rates of C ₅ F ₈ (octafluoro-2-pentyne) and tetraethoxysilane (TEOS) as monomer gases were set to 0.101 Pa · m ³ / sec and 0.0676101 Pa · m ^3. / Sec (volume flow rate ratio 60:40), a film was formed by a plasma CVD method, and a 250 nm organic film 36 was laminated on a fluorinated transparent resin film substrate 404.
Subsequently, a 300 nm-thickness SiO ₂ inorganic film 48 is laminated on the organic film formed in the same manner as in Example 1, and a 250-nm organic film 37 is further laminated in the same manner as described above. A gas barrier substrate 405 having a sealing film was obtained.
On the gas barrier substrate 405, a lithium indium alloy was used, and a lower electrode layer 501 having a thickness of 100 nm was formed by vacuum deposition. 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.
The organic EL light emitting device 903 is formed by sealing the circuit board with the epoxy adhesive 700 on the circuit board 902 with the gas barrier laminate 201 created in the third embodiment.
The evaluation of the light emission lifetime was 4400 hours when the lower electrode layer 501 and the upper electrode layer 502 were applied with a DC voltage, the organic EL light emission lifetime was evaluated, and the half-life was measured.
Comparative Example 6
A circuit board and a light emitting device were prepared in the same manner as in Example 7, without subjecting the cycloolefin polymer film substrate having a thickness of 100 μm used in Example 7 to fluorination treatment, and the light emitting device was fabricated in the same manner as in Example 7. When the organic EL light emission lifetime evaluation was carried out and evaluated, the half-life was 3900 hours.

As described above, a substrate or substrate for a display device such as a liquid crystal display device or an organic EL device, which has a longer light emission life and is required to be thinner, lighter and more flexible; a sealing agent for the display device; Useful.

It is sectional drawing which shows the structure of a typical organic electroluminescent 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. An example in which the gas barrier laminate of the present invention is laminated on a resin substrate having a light emitter, the gas barrier laminate of the present invention is used as a sealing layer, sealed with a sealant, and an organic EL light emitting device is produced is shown. It is sectional drawing. It is the schematic which shows an example of the reaction apparatus used in order to obtain the transparent resin film base material containing the fluorine atom of this invention.

Explanation of symbols

400, 401, 403, 404 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 Example 202: Example of laminate in which inorganic film, organic film and inorganic film are sequentially laminated on resin film substrate 405: Example of laminate in which organic film, inorganic film and organic film are laminated on resin film substrate 901: Organic EL light emitting elements 801, 802, 803, 902: Circuit boards 30, 31, 32, 33, 34, 35, 36, 37 of organic EL light emitting elements: 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: An example of a laminate in which a plurality of organic films and inorganic films are laminated 52: An inorganic film, an organic film, and an inorganic film Multiple membranes Example of laminated body 53: Example of laminated body in which organic film and inorganic film are sequentially laminated on resin film substrate 54: Example of organic film and inorganic film laminated body laminated on resin film substrate 55: Organic film, inorganic film Example of laminate 200: Example of laminate in which organic film and inorganic film laminate are laminated on resin film substrate 201: Example of laminate in which a plurality of organic films and inorganic film laminates are sequentially laminated on resin film substrate 902: Circuit board 203, 204, 901, 903 in which a plurality of organic films and inorganic film laminates are sequentially laminated on a resin film base material: Cross-sectional view of organic EL light emitting device 501: Lower electrode layer 502: Upper electrode layer 601: Light emission Material layer 700: Sealing material of laminate 1: Chamber 2: Fluorine gas supply line 3: Inert gas supply line 4: Exhaust line 5: Heating device 6: Transparent resin film substrate

Claims (11)

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,
The polymer molecule in the surface layer part of the transparent resin film substrate contains a fluorine atom,
The organic film is a film made of a fluorine compound, or a raw material of a fluorine compound and a metal or metalloid simple substance or compound,
A gas barrier laminate in which the inorganic film is a film made of a single metal or a compound as a raw material. The gas barrier laminate according to claim 1, wherein a volume composition ratio F / M of fluorine atoms F and metal atoms M contained in the organic film is 0.01 to 0.99. The gas barrier laminate according to claim 1 or 2, wherein the organic film is formed by a chemical vapor deposition method. 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 any one of claims 1 to 4, wherein the inorganic film is a metal or metalloid compound formed under vacuum. A light emitting device comprising a substrate, a lower electrode layer, a light emitting material layer, an upper electrode layer, and a sealing layer, which are sequentially laminated, wherein the sealing layer is the gas barrier laminate according to claim 1. A light emitting device comprising a substrate, the lower electrode layer, the light emitting material layer, the upper electrode layer, and the sealing layer sequentially laminated, wherein the substrate is the gas barrier laminate according to claim 1. On the transparent resin film substrate, a lower electrode layer, a light emitting material layer, and an upper electrode layer are sequentially laminated, and further, a light emitting element obtained by further laminating at least one organic film and at least one inorganic film thereon,
The polymer molecule in the surface layer portion of the transparent resin film substrate contains a fluorine atom,
The organic film is a film made of a fluorine compound, or a raw material of a fluorine compound and a metal or metalloid simple substance or compound,
A light-emitting element in which the inorganic film is a film made of a single metal or a compound as a raw material. 6. A light emitting device comprising a substrate, a lower electrode layer, a light emitting material layer, an upper electrode layer, and a sealing layer sequentially laminated, wherein the substrate and the sealing layer comprise the gas barrier laminate according to claim 1. . A lower electrode layer, a light emitting material layer, an upper electrode layer and a sealing layer are sequentially laminated on a substrate, and the substrate is the gas barrier laminate according to any one of claims 1 to 5,
The sealing layer is formed by laminating a sealing film formed by laminating at least one organic film and at least one inorganic film,
The organic film is a film made of a fluorine compound, or a fluorine compound and a metal or metalloid simple substance or compound as a raw material,
A light-emitting element in which the inorganic film is a film made of a single metal or a compound as a raw material. The light-emitting element according to any one of claims 6 to 10, wherein the light transmittance at a wavelength of 550 nm when not emitting light is 80% or more.

Images