WO2015033850A1 - Stratifié à film barrière aux gaz, et composant électronique mettant en œuvre celui-ci - Google Patents

Stratifié à film barrière aux gaz, et composant électronique mettant en œuvre celui-ci Download PDF

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Publication number
WO2015033850A1
WO2015033850A1 PCT/JP2014/072573 JP2014072573W WO2015033850A1 WO 2015033850 A1 WO2015033850 A1 WO 2015033850A1 JP 2014072573 W JP2014072573 W JP 2014072573W WO 2015033850 A1 WO2015033850 A1 WO 2015033850A1
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gas barrier
barrier film
film layer
film laminate
laminate according
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PCT/JP2014/072573
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English (en)
Japanese (ja)
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正志 橋本
敦子 藤田
國信 隆史
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Jnc株式会社
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    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40Oxides
    • C23C16/401Oxides containing silicon
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/56After-treatment
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/80Constructional details
    • H10K50/84Passivation; Containers; Encapsulations
    • H10K50/844Encapsulations

Definitions

  • the present invention relates to a gas barrier film laminate.
  • the present invention relates to a gas barrier film laminate that can effectively suppress water vapor permeation to electronic components.
  • OLED elements organic electroluminescent elements
  • OPV elements organic solar cell elements
  • liquid crystal elements and the like.
  • the glass substrate has the disadvantages that it is heavy, easily broken, and difficult to increase in area.
  • a gas barrier film laminate in which a resin composition film in which an inorganic filler is mixed / dispersed on a plastic film or a metal oxide thin film is formed may be used as the substrate.
  • plasma chemical vapor deposition As a method for forming a thin film such as a metal oxide on the surface of a plastic film, plasma chemical vapor deposition (CVD) is particularly known.
  • the plasma CVD method has a problem of a rapid compressive stress generated during the formation of the gas barrier film and the occurrence of curling due to this.
  • Patent Document 1 discloses that a gas barrier layer is an adhesive layer for a first film and a second film in which a gas barrier layer is formed on one surface of a substrate.
  • a gas barrier film laminate having one or more units of a laminated structure formed by bonding with an adhesive layer made of an ultraviolet curable resin is disclosed.
  • the technique of this document is a laminated structure in which a first film and a second film are symmetrically bonded to balance stress.
  • the gas barrier film laminate would inevitably become thick.
  • the present invention has been made in view of the above-described problems of the prior art.
  • the residual stress is relaxed while maintaining flexibility and curling is performed.
  • An object of the present invention is to provide a gas barrier film laminate having a sufficient gas barrier property while being reduced.
  • the inventors of the present invention formed a gas barrier film laminate having low curl and high gas barrier properties by combining a resin film, an organic film layer, and a gas barrier film layer. The present inventors have found that this can be done and have completed the present invention.
  • the gas barrier film laminate according to the first aspect of the present invention includes, for example, as shown in FIG. 1, a resin film 11 as a substrate; at least one organic film layer 12 and at least one on at least one surface of the resin film 11.
  • Two gas barrier film layers 13 are provided; the gas barrier film layer 13 is a film formed by a plasma CVD method and containing an organic component mainly composed of a metal oxide.
  • the “main component” means that the composition constituting the gas barrier film layer contains 50% by weight or more of a portion corresponding to a metal oxide.
  • the gas barrier film laminate according to the second aspect of the present invention is obtained by photopolymerizing the photocurable resin composition in the gas barrier film laminate according to the first aspect of the present invention. Film.
  • the gas barrier film laminate according to the third aspect of the present invention is the gas barrier film laminate according to the second aspect of the present invention, wherein the photocurable resin composition includes an acrylic resin.
  • an organic film layer having excellent transparency can be formed.
  • an acrylic resin having photocurability is preferable because it has excellent curl prevention properties due to its hardness.
  • the gas barrier film laminate according to the fourth aspect of the present invention is the gas barrier film laminate according to any one of the first to third aspects of the present invention, wherein the organic film layer is a coating method. Are stacked.
  • the organic film layer can be uniformly coated, and excellent smoothness can be obtained.
  • the gas barrier film laminate according to the fifth aspect of the present invention is the gas barrier film laminate according to any one of the first to fourth aspects of the present invention, wherein the plasma CVD method comprises a roll, Performed on a two-roll basis.
  • the gas barrier film laminate according to the sixth aspect of the present invention is the gas barrier film laminate according to any one of the first to fifth aspects of the present invention, wherein the thickness of the organic film layer is: 1 to 20 ⁇ m.
  • the gas barrier film laminate according to the seventh aspect of the present invention is the gas barrier film laminate according to any one of the first to sixth aspects of the present invention, wherein the thickness of the gas barrier film layer is: 0.2-2 ⁇ m.
  • the thickness uniformity is improved and the gas barrier performance is improved.
  • production of the crack by bending can be suppressed by setting it as 2 micrometers or less.
  • the gas barrier film laminate according to the eighth aspect of the present invention is the gas barrier film laminate according to any one of the first to seventh aspects of the present invention, wherein the gas barrier film layer is the resin. Provide only on one side of the film.
  • the gas barrier film layer is a gas barrier film laminate provided only on one side of the resin film, the gas barrier film layer has a sufficiently high barrier property and can be made thinner.
  • the gas barrier film laminate according to the ninth aspect of the present invention is the gas barrier film laminate according to any one of the first to eighth aspects of the present invention, wherein the resin film and the organic film are provided. And a curl height of 15 mm or less.
  • the curl height is 15 mm or less, so that the gas barrier film laminate can exhibit good processability.
  • the gas barrier film laminate can exhibit good processability.
  • cracks and film peeling due to curling are suppressed, good gas barrier properties can be maintained.
  • the gas barrier film laminate according to the tenth aspect of the present invention is the gas barrier film laminate according to any one of the first to ninth aspects of the present invention, wherein the organic film layer is the resin film. And the gas barrier film layer.
  • the organic film layer can flatten the irregularities on the surface of the substrate.
  • the gas barrier film laminate according to the eleventh aspect of the present invention is the gas barrier film laminate according to any one of the first to tenth aspects of the present invention, wherein water vapor at 40 ° C. and 90% RH is used.
  • the transmittance is 0.005 g / m 2 / d or less.
  • a gas barrier film laminate according to a twelfth aspect of the present invention is the gas barrier film laminate according to any one of the first to eleventh aspects of the present invention, wherein the resin film is a polyethylene phthalate. , Polyethylene naphthalate, cycloolefin polymer, polycarbonate, polyimide, or a mixture of these as a main component.
  • a resin film can be formed from a resin that is easily available, and a resin suitable for the application, such as being transparent, can be selected as appropriate.
  • An electronic component according to a thirteenth aspect of the present invention is, for example, as shown in FIG. 2B, an electronic element 22 having positive and negative electrodes and an organic material sandwiched between the positive and negative electrodes; And the gas barrier film laminate 10 according to any one of the first to twelfth aspects of the present invention.
  • a gas barrier film laminated body is excellent in gas-barrier property, it can control that water vapor
  • An electronic component according to a fourteenth aspect of the present invention is the electronic component according to the thirteenth aspect of the present invention, wherein the gas barrier film laminate is transparent and the element is an OLED element or an OPV element.
  • the present invention it is possible to provide a gas barrier film laminate having a sufficient gas barrier property while reducing the curl by relaxing the residual stress of the gas barrier film layer formed by the plasma CVD method. Furthermore, the gas barrier film laminate can be used to protect electronic elements such as OLED elements and OPV elements from intrusion of water vapor.
  • FIG. 2A is a cross-sectional view of an electronic component having an OLED element in a solid sealing method.
  • FIG.2 (b) is sectional drawing of the electronic component using the gas barrier film laminated body of this invention as an alternative. It is sectional drawing of the other electronic component using the gas barrier film laminated body of this invention.
  • FIG. 4A is a cross-sectional view of an electronic component having an OLED element with a conventional hollow structure.
  • FIG.4 (b) is sectional drawing of the electronic component using the gas barrier film laminated body of this invention as an alternative. It is the schematic of a roll-to-roll system.
  • the gas barrier film laminate according to the first embodiment of the present invention includes a resin film as a base material, and at least one organic film layer and at least one gas barrier film layer on at least one surface of the resin film.
  • the gas barrier film laminate 10 has an organic film layer 12 directly on the resin film 11, and further has a gas barrier film layer 13 directly on the organic film layer 12.
  • the gas barrier film layer is formed by a plasma CVD method, contains a metal oxide as a main component, and contains an organic component.
  • the gas barrier film layer may be a single film or a composite film.
  • the thickness of the organic film layer is preferably 1 to 20 ⁇ m, more preferably 1.2 to 10 ⁇ m, still more preferably 2 to 8 ⁇ m.
  • the thickness is preferably 1 to 20 ⁇ m, more preferably 1.2 to 10 ⁇ m, still more preferably 2 to 8 ⁇ m.
  • the surface roughness of the organic film layer is preferably an arithmetic average roughness Sa of 5 nm or less, more preferably 3 nm or less, and even more preferably 2 nm or less.
  • the thermal expansion coefficient of the organic film layer is preferably 10 to 150 ⁇ 10 ⁇ 6 / ° C., more preferably 21 to 100 ⁇ 10 ⁇ 6 / ° C., and further preferably 21 to 80 ⁇ 10 ⁇ 6 / ° C. ° C. Although the reason is not clear, curling of the gas barrier film laminate that occurs during the production process of the gas barrier film laminate can be suppressed when it is in the above range.
  • thermal expansion coefficient was measured with a tensile load of 5 g using a thermomechanical test apparatus TMA / SS6100 manufactured by SII Corporation as a measuring apparatus.
  • the temperature range is 25 ° C. to 100 ° C. (temperature increase rate 5 ° C./min, measurement environment: 23 ° C.).
  • the coefficient of thermal expansion was determined from the average value obtained by measuring two samples, approximating the temperature-elongation relationship in a straight line in the above temperature range on the apparatus.
  • Thermal expansion coefficient (linear expansion coefficient) ⁇ ⁇ L / (L ⁇ ⁇ T) ( ⁇ L: sample elongation, L: sample length, ⁇ T: temperature rise)
  • the organic film layer of the present invention is preferably a film obtained by photopolymerizing a photocurable resin composition.
  • the photocurable resin composition is preferably composed of a composition containing an acrylic resin.
  • the “photocurable resin composition” may be a composition that is photocured as a whole, and the photocurable resin does not necessarily have to be a main component.
  • Examples of the photocurable resin that is a precursor of the organic film layer include acrylic resins that can be cured by light such as ultraviolet irradiation.
  • examples thereof include resins having an unsaturated bond capable of radical polymerization, such as (meth) acrylate monomers, unsaturated polyester resins, polyester (meth) acrylate resins, epoxy (meth) acrylate resins, and urethane (meth) acrylate resins. .
  • These acrylic resins can be used alone or in admixture of two or more. Among them, polyester (meth) acrylate resin, urethane (meth) acrylate resin, (meth) acrylate monomer and the like alone or a mixture thereof are preferable.
  • Examples of the (meth) acrylate monomer include compounds obtained by reacting a polyhydric alcohol with an ⁇ , ⁇ -unsaturated carboxylic acid.
  • the condensation product (unsaturated polyester) by esterification reaction of a polyhydric alcohol and unsaturated polybasic acid (and saturated polybasic acid as needed) was melt
  • the unsaturated polyester can be produced by polycondensation of an unsaturated acid such as maleic anhydride and a diol such as ethylene glycol.
  • a polybasic acid having a polymerizable unsaturated bond such as fumaric acid, maleic acid, and itaconic acid or its anhydride is used as an acid component, and ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1, 2 -Butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, cyclohexane
  • Polyhydric alcohols such as 1,4-dimethanol, ethylene oxide adduct of bisphenol A and propylene oxide adduct of bisphenol A are reacted as alcohol components, and phthalic acid, isophthalic acid, terephthalic acid, Such as tetrahydrophthalic acid, adipic acid, sebacic acid Polymerizable not have an unsaturated bond
  • polyester (meth) acrylate resin (1) a terminal carboxyl group polyester obtained from a saturated polybasic acid and / or an unsaturated polybasic acid and a polyhydric alcohol contains an ⁇ , ⁇ -unsaturated carboxylic ester group.
  • saturated polybasic acid used as a raw material for polyester (meth) acrylate examples include polybasic compounds having no polymerizable unsaturated bond such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, and sebacic acid. Examples thereof include acids or anhydrides thereof and polymerizable unsaturated polybasic acids such as fumaric acid, maleic acid and itaconic acid or anhydrides thereof. Further, the polyhydric alcohol component is the same as the unsaturated polyester.
  • the epoxy (meth) acrylate resin includes a polymerizable unsaturated bond formed by a ring-opening reaction between a compound having a glycidyl group (epoxy group) and a carboxyl group of a carboxyl compound having a polymerizable unsaturated bond such as acrylic acid.
  • the vinyl ester is produced by a known method, and includes an epoxy (meth) acrylate obtained by reacting an epoxy resin with an unsaturated monobasic acid such as acrylic acid or methacrylic acid.
  • epoxy resins may be reacted with bisphenol (for example, A type) or dibasic acid such as adipic acid, sebacic acid, dimer acid (Haridimer 270S: Harima Kasei Co., Ltd.) to impart flexibility.
  • bisphenol for example, A type
  • dibasic acid such as adipic acid, sebacic acid, dimer acid (Haridimer 270S: Harima Kasei Co., Ltd.
  • examples of the epoxy resin as a raw material include bisphenol A diglycidyl ether and its high molecular weight homologues, novolak glycidyl ethers, and the like.
  • urethane (meth) acrylate resin for example, after reacting a polyisocyanate with a polyhydroxy compound or a polyhydric alcohol, a hydroxyl group-containing (meth) acrylic compound and, if necessary, a hydroxyl group-containing allyl ether compound are reacted. And a radical-polymerizable unsaturated group-containing oligomer that can be obtained.
  • polyisocyanates include 2,4-tolylene diisocyanate and its isomers, diphenylmethane diisocyanate, hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, triphenyl.
  • Methane triisocyanate Bannock D-750, Crisbon NK (trade name; manufactured by DIC Corporation), Desmodur L (trade name; manufactured by Sumitomo Bayer Urethane Co., Ltd.), Coronate L (trade name; Nippon Polyurethane Industry Co., Ltd.) Manufactured), Takenate D102 (trade name; manufactured by Mitsui Takeda Chemical Co., Ltd.), Isonate 143L (trade name; manufactured by Mitsubishi Chemical Corporation), and the like.
  • the polyhydroxy compound include polyester polyol and polyether polyol.
  • glycerin-ethylene oxide adduct examples include oxide adducts.
  • polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 2-methyl-1,3-propanediol, and 1,3-butane.
  • the hydroxyl group-containing (meth) acrylic compound is not particularly limited, but a hydroxyl group-containing (meth) acrylic acid ester is preferable, and specific examples thereof include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl.
  • (Meth) acrylate, 3-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, di (meth) acrylate of tris (hydroxyethyl) isocyanuric acid, pentaerythritol tri (meth) An acrylate etc. are mentioned.
  • the photocurable resin composition contains a photopolymerization initiator.
  • a photoinitiator if it is a compound which generate
  • Photopolymerization initiators include benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy -2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2 -Dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, -Benzyl-2-dimethylamino-1- (4-
  • These compounds may be used alone or in combination of two or more.
  • the amount of the polymerization initiator used in the above addition polymerization is preferably about 0.01 to 10 mol% based on the total number of moles of monomers. These photopolymerization initiators can be used alone or in combination of two or
  • a chain transfer agent may be used.
  • the molecular weight can be appropriately controlled by using the chain transfer agent.
  • chain transfer agents include thio- ⁇ -naphthol, thiophenol, butyl mercaptan, ethyl thioglycolate, mercaptoethanol, mercaptoacetic acid, isopropyl mercaptan, t-butyl mercaptan, dodecanethiol, thiomalic acid, pentaerythritol tetra (3 -Mercaptans such as mercaptopropionate) and pentaerythritol tetra (3-mercaptoacetate); disulfides such as diphenyl disulfide, diethyl dithioglycolate and diethyl disulfide; and the like, toluene, methyl isobutyrate, Carbon tetrachloride, isopropylbenzene, dieth
  • Solvents used when preparing a coating solution in which a photocurable resin is dissolved or dispersed in a solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, ⁇ - or ⁇ - Terpenes such as terpineol, etc., ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, diethyl ketone, 2-heptanone, 4-heptanone, aroma such as toluene, xylene, tetramethylbenzene Aromatic hydrocarbons, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glyco
  • a coating solution in which a photocurable resin is dissolved or dispersed in a solvent improves the surface fluidity and leveling properties of the coating solution applied at the time of coating, and prevents pinholes and defects in the coating film due to poor wetting and repellency.
  • a surface conditioner leveling agent, wettability improving agent, interfacial slipping agent, etc.
  • the surface conditioner include polysiloxane, polyacrylate and wax.
  • an additive such as an antifoaming agent for preventing the generation of bubbles in the coating solution may be used.
  • antifoaming agents include mineral oil compounds and polysiloxane compounds.
  • the method for forming the organic film layer is not particularly limited, but it is preferable to use a wet coating method (coating method) in order to uniformly coat the photocurable resin composition.
  • a wet coating method coating method
  • excellent surface smoothness can be obtained.
  • the coating methods when a small amount is prepared, a spin coating method capable of simple and uniform film formation is preferable. In the case of roll-to-roll, where productivity is important, gravure coating method, die coating method, reverse coating method, roll coating method, slit coating method, dipping method, spray coating method, kiss coating method, reverse kiss coating method, air A knife coating method, a curtain coating method, a rod coating method and the like are preferable.
  • the coating method can be appropriately selected from these methods according to the required film thickness, viscosity, curing conditions, and the like.
  • the applied coating solution can be dried with hot air or the like in an environment of room temperature to about 200 ° C.
  • a photoactive energy beam or an electron beam is irradiated and cured by an active energy beam source.
  • an active energy beam source there is no particular limitation as a photoactive energy ray source, depending on the nature of the photopolymerization initiator used, for example, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a carbon arc, a xenon arc, a gas laser, a solid laser, An electron beam irradiation apparatus etc. are mentioned.
  • the drying furnace passage time for drying differs depending on the line speed, the type of coating liquid, the coating thickness, and the apparatus capacity (air volume, area, etc.). For example, 1 to 105 minutes can be mentioned. Similarly, the amount of irradiation for curing varies depending on the material and thickness. For example, when a high-pressure mercury lamp is used, about 200 to 700 mJ / cm 2 can be mentioned.
  • the gas barrier film layer included in the gas barrier film laminate is a film containing metal oxide as a main component, formed by a plasma CVD method, and is a single film or a composite film. Note that a film mainly containing a metal nitride or a mixture of a metal oxide and a metal nitride may be used instead of the metal oxide.
  • the thickness of the gas barrier film layer is preferably 0.2 to 2 ⁇ m, more preferably 0.3 to 1.5 ⁇ m, still more preferably 0.5 to 1.5 ⁇ m.
  • the thickness is 0.2 ⁇ m or more, the film thickness uniformity is good and the gas barrier performance is excellent. If it is 2 ⁇ m or less, cracks due to bending are less likely to occur.
  • PVD physical vapor deposition
  • CVD chemical vapor deposition
  • the vacuum deposition method is widely used as a highly productive process, but the gas barrier performance is inferior.
  • a dense film can be formed by sputtering, the film formation rate is low and sufficient productivity cannot be obtained.
  • the film formed by the PVD method is inorganic and brittle, defects and peeling are likely to occur, and high barrier properties cannot be imparted.
  • the plasma CVD method has an advantage in terms of productivity as compared with the sputtering method, and further has a good gas barrier performance as compared with the vacuum evaporation method and the sputtering method.
  • the plasma CVD method can be preferably used as the method for forming the gas barrier film layer. More preferably, a roll-to-roll type plasma CVD method can be used in terms of productivity and quality stability.
  • CVD Chemical Vapor Deposition
  • one or more source gases of a compound containing a constituent element of a thin film material to be manufactured are supplied onto a film formation target (for example, a substrate), and the gas phase or the surface of the substrate is supplied.
  • the plasma CVD method is a method in which a reactive gas is brought into a plasma state, active radicals and ions are generated, and a chemical reaction is performed in an active environment.
  • the roll-to-roll means that a film-forming object wound in a roll shape is sent out from a feed roll 31, and a target substance is formed on a surface and printed, and another roll (winding is wound again).
  • This is a production method in which a take-up reel 32) is wound up and collected.
  • Japanese Patent Publication No. 2005-504880 includes a pair of film forming rolls that wind and convey a film to be formed, forms a magnetic field across the rolls, and the two film forming rolls are the same.
  • HMDSO hexamethyldisiloxane
  • Japanese Patent No. 2587507 discloses a pair of film forming rolls (metal drums) arranged facing each other in a vacuum chamber, an AC power source in which one and the other electrode are connected to one and the other film forming rolls, respectively.
  • a plasma CVD film forming apparatus having a discharge chamber disposed in an opposing space between film forming rolls and having a surface facing the film forming roll opened, and a monomer (raw material) gas supply means connected to the discharge chamber is described. Has been.
  • a pulse voltage accompanied by alternating current or polarity reversal is applied to the film forming rolls arranged to face each other under reduced pressure, and a facing space (film forming zone) between the film forming rolls arranged opposite to each other.
  • a device for generating a film by plasma CVD on a belt-like base material wound around facing a facing space of a film forming roll As an example, a plasma CVD apparatus (Roll coater W35) manufactured by Kobe Steel, Ltd. can be preferably used.
  • Examples of the metal oxide that is the main component of the gas barrier film layer include silicon oxide, aluminum oxide, and titanium oxide. In applications where transparency is required for the gas barrier film laminate, silicon oxide is more preferable.
  • the source gas used for forming the gas barrier film layer is preferably an organometallic compound.
  • an organosilicon compound containing silicon, an organoaluminum compound containing aluminum, or the like can be used.
  • these raw material gases it is more preferable to use an organosilicon compound from the viewpoints of handling of the compound and imparting flexibility and high gas barrier properties to the resulting gas barrier film layer.
  • organosilicon compounds include HMDSO, 1.1.3.3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethoxysilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyl Examples include triethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, and octamethylcyclotetrasiloxane.
  • organosilicon compounds HMDSO, 1.1.3.3-tetramethyldisiloxane, and tetraethoxysilane are particularly preferable from the viewpoints of properties such as compound handling properties and gas barrier properties of the obtained thin film layer.
  • These raw materials such as organosilicon compounds can be used singly or in combination of two or more.
  • the organoaluminum compound include trimethylaluminum.
  • a reactive gas can be used.
  • a gas that reacts with the raw material gas and its radical to become a compound such as an oxide or a nitride can be used.
  • the reaction gas for example, oxygen, nitrogen, ammonia, ozone, or the like can be used. These reaction gases can be used alone or in combination of two or more.
  • a carrier gas may be used as necessary.
  • a discharge gas may be used as necessary in order to generate plasma discharge.
  • carrier gas and discharge gas known ones can be used as appropriate, and for example, rare gases such as helium, argon, neon, xenon, and the like can be used.
  • Such gases for film formation gases used during film formation (gases used during film formation such as source gas, reaction gas, carrier gas, discharge gas) are collectively referred to as “film formation gas”.
  • the mixing ratio of the reaction gas to the raw material gas is such that the molar amount of the reaction gas used is A ⁇ when the molar ratio of the reaction gas that is theoretically necessary for complete reaction with 1 mol of the raw material gas is A.
  • a range of (0.2 to 1.5) is preferable, and a range of A ⁇ (0.3 to 1.25) is more preferable.
  • a gas barrier film layer is formed by reacting a film forming gas containing HMDSO as a source gas and oxygen (O 2 ) as a reaction gas by plasma CVD, the reaction is described in the following reaction formula (1).
  • the ratio of the reaction gas is too low, an organic component derived from the source gas in the formed barrier film (for example, when HMDSO is used as the source gas, a component containing carbon due to the methyl group contained in the source material) ) And a high barrier property cannot be obtained, and if the ratio of the reaction gas is too high, the reaction proceeds too much and the barrier film becomes brittle and the flexibility and durability are poor.
  • the pressure (degree of vacuum) in the vacuum chamber of the plasma CVD apparatus can be appropriately adjusted according to the type of the raw material gas, but is preferably in the range of 0.1 Pa to 50 Pa.
  • the electric power applied for discharging can be adjusted as appropriate according to the type of source gas, the pressure in the vacuum chamber, etc., but is preferably in the range of 0.2 to 10 kW.
  • the applied power is equal to or higher than the lower limit, the reaction of the raw material gas is not insufficient and the barrier property is not lowered. As a result, wrinkles are not generated on the object of film formation, and irregularities are generated on the film surface and the appearance is not impaired.
  • the conveyance speed of the film forming target can be appropriately adjusted according to the type of source gas, the pressure in the vacuum chamber, etc., but is preferably in the range of 0.1 to 50 m / min, preferably 0.3 to 20 m. / Min is more preferable.
  • the line speed is equal to or higher than the lower limit, wrinkles due to heat tend not to occur in the resin film being conveyed.
  • the line speed is equal to or lower than the upper limit, the thickness of the formed thin film layer does not become too thin.
  • the gas barrier film layer contains an organic component.
  • a thin film is formed by a plasma CVD method from a film forming gas (mixed gas of HMDSO as a source gas and oxygen gas as a reaction gas (also functioning as a discharge gas)) and a gas barrier film layer is formed, the following reaction formula is obtained.
  • the formed film contains Cy (a trace amount of carbon component) as an organic component. (CH 3 ) 3 Si—O—Si (CH 3 ) 3 + O 2 ⁇ SiOxCy (2)
  • Resin film used as a base material of a gas barrier film laminated body will not be specifically limited if it is formed with the organic material which can hold
  • polyethylene terephthalate PET
  • polybutylene terephthalate polyethylene naphthalate
  • PC polycarbonate
  • PVC polyvinyl chloride
  • PE polyethylene
  • PP polypropylene
  • PS polystyrene
  • nylon Ny
  • cycloolefin polymer aromatic polyamide, polyether ether ketone, polysulfone, polyether sulfone, acrylic ester polymer, methacrylic ester polymer, polyimide, polyetherimide, etc.
  • the thickness of the resin film is not particularly limited, but is preferably 20 to 500 ⁇ m, more preferably 30 to 300 ⁇ m.
  • the thickness is 20 ⁇ m or more, the rigidity as a base material is insufficient, and stability does not decrease during film formation on a roll-to-roll basis. Moreover, if it is 500 micrometers or less, it can avoid that a flexibility falls and it becomes cost up.
  • the resin film when the resin film is transparent, the organic film layer and the gas barrier film layer formed on the resin film are also transparent, so that a transparent gas barrier film laminate can be obtained. Therefore, a transparent substrate such as an OLED element or an OPV element can be used, which is more preferable.
  • the surface (resin film surface, organic film layer surface, gas barrier film layer surface) of the gas barrier film laminate according to the present invention is subjected to surface modification treatment such as corona treatment or plasma treatment for the purpose of improving adhesion. Also good.
  • the gas barrier film laminate of the present invention has at least one organic film layer and at least one gas barrier film layer on at least one side of the resin film, and the resin film and the organic film layer are preferably in contact with each other. More preferably, as shown in FIG. 1, a gas barrier film laminate 10 having a structure in which an organic film layer 12 and a gas barrier film layer 13 are laminated only on one side of a resin film 11.
  • a gas barrier film laminate 10 having a structure in which an organic film layer 12 and a gas barrier film layer 13 are laminated only on one side of a resin film 11.
  • the gas barrier film layer has a structure that is laminated only on one side of the resin film, so that the weight of the gas barrier film laminate is improved, the light transmittance is improved, and the manufacturing process is simplified compared to the case where it is laminated on both sides. It is possible to achieve the above and more preferable.
  • the gas barrier film laminate formed by the configuration of the present invention has a high gas barrier with a water vapor transmission rate (temperature: 40 ⁇ 0.5 ° C., relative humidity: 90 ⁇ 5% RH) of 0.005 g / m 2 / d or less. Expresses sex. By optimizing the film formation conditions, 0.001 g / m 2 / d or less can be developed, and by optimizing the thickness of the organic film layer and gas barrier film layer, 0.0001 g / m 2 / d or less Is achieved.
  • the gas barrier film laminate of the present invention is preferably composed of only a transparent material when used for applications such as a photoelectric element, an OLED element, or an OPV element, and has a total light transmission measured according to the JIS 7105 method.
  • the rate is preferably 80% or more, more preferably 85% or more, and particularly preferably 88% or more.
  • an opaque gas barrier film laminate may be produced.
  • the gas barrier film laminate of the present invention suppresses the internal stress that tends to curl in the use environment as much as possible, and exhibits good curl prevention properties. Thereby, after manufacturing the said gas barrier film laminated body, when passing through other processes, such as an assembly process to a device, favorable workability is exhibited. Further, there is no crack or film peeling due to curling, and good gas barrier properties can be maintained.
  • the gas barrier film laminate of the present invention laminated on a 125 ⁇ m-thick PET film is cut to 100 mm ⁇ 100 mm and placed on a surface plate, and from a surface plate surface using a height measuring instrument such as a ruler.
  • the curl height is preferably 15 mm or less, more preferably 10 mm or less, and particularly preferably 5 mm or less.
  • the “curl height” is an average of the heights of the four corners of a square film.
  • the gas barrier film laminate of the present invention can be used for applications that require blocking of various gases such as water vapor and oxygen. Particularly preferably, it can be usefully used for blocking various gases such as OLED elements or OPV elements.
  • a gas barrier film laminated body is transparent, when it uses for a photoelectric element like an OPV element, it can comprise so that sunlight reception may be performed from the gas barrier film laminated body side. Further, when used in an OLED element, light emission from the element is not hindered, so that the light emission efficiency is not deteriorated.
  • FIG. 2A shows a schematic diagram of an electronic component having an OLED element in a solid sealing system.
  • An OLED element 22 having positive and negative electrodes and an organic material sandwiched between the positive and negative electrodes is disposed on a glass substrate 21, and the OLED element 22 is entirely covered with a solid sealing agent 23.
  • the gas barrier film laminate 10 of the present application can be used instead of the glass substrate 21 as shown in FIG. Or as shown in FIG. 3, it is good also as a sandwich structure which pinched
  • FIG. 4A shows a schematic diagram of an electronic component having an OLED element with a conventional hollow structure.
  • An OLED element 22 having positive and negative electrodes and an organic material sandwiched between the positive and negative electrodes is disposed on the glass substrate 21 and covered with a glass sealing material 28 that is present at a distance.
  • the glass substrate 21 and the glass sealing material 28 are bonded (sealed) with an adhesive 25 on both sides.
  • a getter 26 that adsorbs moisture is disposed inside the hollow and is filled with N 2 gas 27.
  • the gas barrier film laminate 10 of the present application can be used as an alternative to the glass base material 21 and the glass sealing material 28 as shown in FIG.
  • the gas barrier film laminate of the present application can be similarly used as an alternative to a glass substrate.
  • the gas barrier film laminate of the present invention when used as a transparent substrate for OLED elements, OPV elements, liquid crystal elements, etc., it is possible to meet the demands for weight reduction and size increase. Furthermore, roll-to-roll (feeding a substrate such as a resin film wound in a roll shape, processing the target substance on the surface of the substrate, etc., and then winding it up again to collect it In place of glass substrates that are heavy, easy to break, and difficult to increase in area. Can be satisfied.
  • film base materials such as transparent plastics have a problem that gas barrier properties are inferior to glass, but when the gas barrier film laminate of the present invention is used, for example, electronic components such as OLED elements and OPV elements When used as a material, the substrate having excellent gas barrier properties can prevent water (water vapor) or oxygen from permeating and degrading components constituting the device, thereby reducing performance.
  • the present invention mainly includes display elements typified by organic electroluminescence elements (OLED elements) and liquid crystal elements, photoelectric elements typified by organic solar cell elements (OPV elements), illumination using OLED elements, and the like. It is a gas barrier film laminated body which can be used for the product.
  • the gas barrier film laminate of the present invention is characterized by good productivity, low curl, and good gas barrier properties.
  • the produced gas barrier film laminate was evaluated for bending resistance based on JIS K5600-5-1 (cylindrical mandrel method).
  • ⁇ Curl test> The produced gas barrier film laminate was allowed to stand for 1 day or longer in an environment of 23 ⁇ 2 ° C. and 50 ⁇ 10% RH while being wound into a roll. Then, it cut
  • JIS 1 grade metal ruler JIS 1 grade metal ruler
  • the method for measuring the water vapor transmission rate is not particularly limited, but in the present invention, evaluation was performed by the method described in ISO 15106-3 or the Ca corrosion method described below.
  • Measurement method 1 ISO 15106-3 method
  • Evaluation apparatus Illinois water vapor permeability measuring apparatus Model 7002
  • Temperature and humidity 40 ° C, 90% RH ⁇
  • Measurement method 2 Ca corrosion method
  • the measurement method 1 was below the measurement limit, the measurement was performed by the following method.
  • the water vapor transmission rate is calculated from the corrosion area and the time to reach the corrosion area.
  • the evaluation was performed by the method described in Japanese Patent No. 3958235 and the following conditions.
  • -Ca method used for evaluation of the present invention Vapor deposition apparatus: Electron beam vacuum deposition apparatus SVC-700LEB manufactured by Sanyu Electronics Co., Ltd. Constant temperature and humidity chamber: Espec Co., Ltd.
  • LHL-113 Metal that reacts with water and corrodes Calcium (granular) Water vapor impermeable metal for Ca sealing: Aluminum ( ⁇ 3-5mm, granular) Sealing material: mixture of paraffin (melting point 60-62 ° C) / beeswax (melting point 61-65 ° C) in a weight ratio of 1: 1 Observation device: Calcium corrosion observation device MFB-1000 manufactured by Mitsuwa Frontec Co., Ltd.
  • Example 1 -Base material
  • PET polyethylene terephthalate
  • COSMO SHINE A4300 manufactured by Toyobo Co., Ltd.
  • Example 2 Preparation of coating solution for photocurable resin composition
  • a gas barrier film laminate was prepared in the same manner as in Example 1 except that the coating liquid for the photocurable resin composition was prepared.
  • Example 3 A gas barrier film laminate was prepared in the same manner as in Example 2 except that the gas barrier film layer formed by plasma CVD was processed to have the thickness shown in Table 1.
  • Example 4 A gas barrier film laminate was prepared in the same manner as in Example 2 except that the organic film layer by the gravure coater was processed so that the thickness after drying was as shown in Table 1.
  • Example 5 Example 2 except that a polyethylene naphthalate (PEN) film (trade name “Teonex Q65FA” manufactured by Teijin DuPont Films Ltd.) wound in a roll shape with a thickness of 125 ⁇ m and a width of 550 mm was used as the substrate. Similarly, a gas barrier film laminate was prepared.
  • PEN polyethylene naphthalate
  • the gas barrier film laminate of the present invention has high barrier properties while curling is reduced.
  • the present invention mainly relates to a gas barrier film laminate used for an electronic component having an OLED element, an OPV element, a liquid crystal element, and the like, and an electronic component including the gas barrier film laminate.

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  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

Selon l'invention, par formation d'une membrane barrière aux gaz au moyen d'un dépôt chimique en phase vapeur assisté par plasma, il est possible d'obtenir un stratifié à film barrière aux gaz dont les propriétés de flexibilité sont préservées, la contrainte résiduelle est atténuée et l'ondulation est réduite, et qui simultanément possède des propriétés de barrière aux gaz suffisantes. Le stratifié à film barrière aux gaz de l'invention, est équipé : d'un film de résine (11) servant de matériau de base ; et sur au moins une face du film de résine (11), d'au moins une couche de membrane organique (12), et d'au moins une couche de membrane de barrière aux gaz (13). La couche de membrane de barrière aux gaz (13) consiste en une membrane fabriquée par dépôt chimique en phase vapeur assisté par plasma, ayant un oxyde métallique pour composant principal, et comprenant un composant organique.
PCT/JP2014/072573 2013-09-03 2014-08-28 Stratifié à film barrière aux gaz, et composant électronique mettant en œuvre celui-ci WO2015033850A1 (fr)

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US11319613B2 (en) 2020-08-18 2022-05-03 Enviro Metals, LLC Metal refinement

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WO2019188771A1 (fr) * 2018-03-27 2019-10-03 住友化学株式会社 Film stratifié

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JP2008235165A (ja) * 2007-03-23 2008-10-02 Konica Minolta Holdings Inc 透明導電膜を有するロール状樹脂フィルムの製造方法
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JP2012097354A (ja) * 2010-10-08 2012-05-24 Sumitomo Chemical Co Ltd 積層体の製造方法
WO2012067186A1 (fr) * 2010-11-19 2012-05-24 コニカミノルタホールディングス株式会社 Procédé de fabrication pour un film barrière contre les gaz et film barrière contre les gaz
JP2013086445A (ja) * 2011-10-21 2013-05-13 Konica Minolta Advanced Layers Inc ガスバリア性フィルム、ガスバリア性フィルムの製造方法、及びガスバリア性フィルムを有する電子デバイス

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JP2006044231A (ja) * 2004-06-28 2006-02-16 Dainippon Printing Co Ltd ガスバリア性フィルム、並びにこれを用いたディスプレイ用基板及びディスプレイ
JP2008235165A (ja) * 2007-03-23 2008-10-02 Konica Minolta Holdings Inc 透明導電膜を有するロール状樹脂フィルムの製造方法
JP2011116124A (ja) * 2009-10-30 2011-06-16 Sumitomo Chemical Co Ltd 積層フィルムの製造方法
JP2012097354A (ja) * 2010-10-08 2012-05-24 Sumitomo Chemical Co Ltd 積層体の製造方法
WO2012067186A1 (fr) * 2010-11-19 2012-05-24 コニカミノルタホールディングス株式会社 Procédé de fabrication pour un film barrière contre les gaz et film barrière contre les gaz
JP2013086445A (ja) * 2011-10-21 2013-05-13 Konica Minolta Advanced Layers Inc ガスバリア性フィルム、ガスバリア性フィルムの製造方法、及びガスバリア性フィルムを有する電子デバイス

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Publication number Priority date Publication date Assignee Title
US11319613B2 (en) 2020-08-18 2022-05-03 Enviro Metals, LLC Metal refinement
US11578386B2 (en) 2020-08-18 2023-02-14 Enviro Metals, LLC Metal refinement

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