WO2018180410A1 - Insulation film laminated metal plate and metal substrate - Google Patents

Insulation film laminated metal plate and metal substrate Download PDF

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Publication number
WO2018180410A1
WO2018180410A1 PCT/JP2018/009414 JP2018009414W WO2018180410A1 WO 2018180410 A1 WO2018180410 A1 WO 2018180410A1 JP 2018009414 W JP2018009414 W JP 2018009414W WO 2018180410 A1 WO2018180410 A1 WO 2018180410A1
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Prior art keywords
insulating film
metal plate
derived unit
polyol
acid
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PCT/JP2018/009414
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French (fr)
Japanese (ja)
Inventor
平野　康雄
陽子 志田
水野　雅夫
渡瀬　岳史
山本　哲也
辰彦 岩
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株式会社神戸製鋼所
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Application filed by 株式会社神戸製鋼所 filed Critical 株式会社神戸製鋼所
Priority to KR1020197031612A priority Critical patent/KR102338975B1/en
Priority to CN201880019455.4A priority patent/CN110494281B/en
Priority to MYPI2019005724A priority patent/MY193148A/en
Publication of WO2018180410A1 publication Critical patent/WO2018180410A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/41—Organic pigments; Organic dyes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
    • H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/26—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to an insulating film laminated metal plate and a metal substrate. More specifically, the present invention relates to an insulating film laminated metal plate and a metal substrate used for a top emission type organic EL element or a substrate type thin film solar cell.
  • Organic semiconductors are flexible and can be made thin, and they are power-saving, so they are expected to be applied to organic electronic devices such as top emission type organic EL (electroluminescence) elements and substrate type thin film solar cells.
  • the organic EL element includes a light emitting layer containing an organic semiconductor, and further includes an anode made of ITO (indium tin oxide) having both transparency and conductivity, and a cathode made of, for example, IZO (indium zinc oxide).
  • the solar cell includes a photoelectric conversion layer made of an organic semiconductor, and further includes a back electrode and a front electrode made of ITO, for example.
  • Patent Document 1 discloses an insulating film laminated metal plate having a surface roughness of 30 nm or less, a film thickness of 10 to 40 ⁇ m, and a single film containing polyester as a thermosetting resin laminated on the surface of the metal plate. Is disclosed. Further, Patent Document 2 includes one or more thermosetting resin coating layers on one or both sides of a metal plate, and the resin coating layer has a surface roughness of 20 nm or less and a total film thickness of 1 to 30 ⁇ m. In addition, an insulating film laminated metal plate whose main resin is a polyester resin is disclosed.
  • the organic EL element is obtained by laminating the anode, the light emitting layer, and the cathode in this order on the insulating film of the insulating film laminated metal plate.
  • the organic EL element is installed in the light emitting circuit and a current is passed, the light emitting layer emits light.
  • the solar cell can be obtained by laminating the back electrode, the photoelectric conversion layer, and the front electrode in this order on the insulating film of the insulating film laminated metal plate.
  • JP 2014-208479 A Japanese Unexamined Patent Publication No. 2016-193580
  • the organic EL element When the organic EL element is fabricated using the insulating coating laminated metal plate disclosed in Patent Document 1 and Patent Document 2 to emit light, the organic EL element has a width of 5 to 10 ⁇ m as shown in FIG. It may emit light with a bright and dark striped pattern with a length of 20 to 50 ⁇ m.
  • An organic EL element that emits light with such a striped pattern causes color unevenness and insufficient light emission illuminance as compared with an organic EL element that emits light uniformly on the surface of the light emitting layer, and does not satisfy the required performance as an organic EL element. .
  • the light emission having the striped pattern is a wrinkle generated on the surface of the conductive thin film layer when the conductive thin film layer is formed on the insulating film of the insulating film laminated metal plate by sputtering. caused by.
  • the present invention has been made in view of the above circumstances, and it is possible to suppress the generation of wrinkles on the surface of the conductive thin film layer and the insulating film laminated metal plate capable of suppressing the generation of wrinkles when forming the conductive thin film layer by sputtering.
  • An object of the present invention is to provide a finished metal substrate.
  • thermosetting resin is A polyester resin comprising a dicarboxylic acid-derived unit containing 90 mol% or more of terephthalic acid-derived units and isophthalic acid-derived units in total, and a polyol-derived unit containing 90 mol% or more of a polyol-derived unit having 2 to 5 carbon atoms.
  • the adjusted average carbon number of the polyol-derived unit calculated by the following formula (1) is 3.4 or less, for forming a conductive thin film layer on the insulating film.
  • Another aspect of the present invention is a metal substrate in which a conductive thin film layer is laminated on an insulating film of the insulating film laminated metal plate.
  • FIG. 1 is a photo, which substitutes for a drawing, showing an optical microscope image of a light emission state on the surface of a top emission type organic EL device manufactured using a conventional insulating coating laminated metal plate.
  • FIG. 2 is a drawing-substituting photograph showing an atomic force microscope image of the surface of an ITO layer on one metal substrate.
  • FIG. 2 is a drawing-substituting photograph showing an atomic force microscope image of the surface of an ITO layer in a metal substrate of FIG.
  • the insulating film laminated metal plate is first cleaned, and an ITO layer serving as an anode is laminated on the insulating film by sputtering. To do. Thereby, the metal substrate which has an ITO layer as an electroconductive thin film layer is obtained. Next, a hole injecting / transporting layer, a light emitting layer, and an electron transporting layer are laminated on the ITO layer by depositing or applying and heating each layer raw material composition in this order. Subsequently, an IZO layer as a cathode is formed on the electron transport layer by sputtering.
  • the thicknesses of these layers are set to values of several tens to several hundreds of nanometers, respectively. .
  • the thickness of the IZO layer constituting the cathode is also set to a value from several tens of nm to several hundreds of nm.
  • FIG. 1 is a drawing-substituting photograph showing an optical microscope image of a light emission state on the surface of the OLED element in which the color unevenness occurs.
  • the OLED element that emits light with such a striped pattern has not only low emission illuminance, but also shortens the lifetime of the strongly emitting portion in the light emitting layer, compared with the OLED element that emits light uniformly over the entire surface. It has also been found that the lifetime as an OLED element tends to be relatively short due to the above.
  • the inventors of the present invention diligently studied the cause of the OLED element in which the color unevenness is caused to exhibit the above-described bright and dark stripe pattern. And the cause is that when the ITO layer is formed, wrinkles having a height difference of several tens to several hundreds of nanometers occur on the surface of the ITO layer, and the wrinkles are thin hole injection / transport layers, light emission It was ascertained that it was reflected on the device surface through the layer, the electron transport layer, and the IZO layer.
  • the wrinkles on the surface of the ITO layer are affected by the heat of sputtering, and the insulating film located below the ITO layer rises to about 200 to 250 ° C. according to the estimated value based on the energy calculation. Presumed to have occurred due to softening.
  • a wrinkle is a convex group (a plurality of lines) having a length of 20 to 50 ⁇ m, a width of 5 to 10 ⁇ m and a height (height difference between peaks and valleys) of 100 nm or more formed on the surface layer of the object to be observed.
  • (Ridge line) which refers to the unevenness observed when the surface of the object to be observed is observed with an atomic force microscope.
  • FIG. 2 is a drawing-substituting photograph showing an atomic force microscope image of the surface of an ITO layer in a metal substrate of FIG.
  • the molar percentage of the terephthalic acid-derived unit in the dicarboxylic acid-derived unit refers to the percentage of the molar part of the terephthalic acid-derived unit with respect to 100 mol part of the dicarboxylic acid-derived unit.
  • the insulating film laminated metal plate of the present invention has a metal plate and an insulating film laminated on at least one surface side of the metal plate.
  • the insulating film contains a thermosetting resin.
  • the thermosetting resin includes a dicarboxylic acid-derived unit containing 90 mol% or more of terephthalic acid-derived units and isophthalic acid-derived units, and a polyol-derived unit containing 90 mol% or more of a polyol-derived unit having 2 to 5 carbon atoms.
  • the polyester resin comprised from these is contained.
  • the molar percentage of the terephthalic acid-derived unit in the dicarboxylic acid-derived unit is 40 to 70%.
  • the mole percentage of the isophthalic acid-derived unit in the dicarboxylic acid-derived unit is 30 to 60%.
  • the adjusted average carbon number of the polyol-derived unit calculated by the above formula (1) is 3.4 or less.
  • the insulating film laminated metal plate of the present invention is used to form a conductive thin film layer on the insulating film.
  • the metal plate used for the insulating coating laminated metal plate of the present invention is a cold-rolled steel plate, a hot-dip galvanized steel plate, an alloyed hot-dip Zn-Fe-plated steel plate, an alloyed hot-melt Zn-5% Al-plated steel plate, a hot 55% Al -Zn alloy-plated steel sheet, electro-pure galvanized steel sheet, electro-Zn-Ni plated steel sheet, aluminum plate, titanium plate or the like.
  • an untreated material (so-called bare plate) whose surface is not chemically treated can be used.
  • the metal plate a chromate material whose surface is subjected to chromate treatment or a non-chromate material whose surface is subjected to non-chromate treatment is used. It is preferable to use it. From the viewpoint of environmental conservation, it is more preferable to use a non-chromate material as the metal plate.
  • the thickness of the metal plate is not particularly limited. The thickness is, for example, about 0.3 to 2.0 mm depending on the use of the insulating film laminated metal plate.
  • an insulating film has electrical insulation. More specifically, when an organic electronic device manufactured using the insulating film laminated metal plate of the present invention is used, the insulating film has an electrical insulation property that prevents current from leaking from the layer located immediately above the metal plate. .
  • the insulating film is laminated on one side or both sides of the metal plate depending on the application of the insulating film laminated metal plate.
  • the insulating film may be laminated directly on the metal plate, or may be laminated on the metal plate via another layer. By laminating the insulating film on the metal plate, electrical insulation between the metal plate and a layer (for example, a conductive thin film layer) laminated on the upper side of the insulating film is ensured.
  • the thickness of the insulating film is not particularly limited, but it is preferable that the thickness of the insulating film is 10 ⁇ m or more from the viewpoint of stably ensuring the electrical insulation of the insulating film. On the other hand, when the thickness of the insulating film exceeds 50 ⁇ m, the electric insulating property of the insulating film tends to be saturated, and therefore the thickness of the insulating film is preferably 50 ⁇ m or less.
  • the insulating film mainly contains a thermosetting resin.
  • the insulating film is formed of, for example, titanium oxide as described later in order to adjust the light emission color of an organic electronic device produced using the insulating film laminated metal plate according to the use of the insulating film laminated metal plate.
  • the insulating film contains a pigment, light having a specific wavelength among the light transmitted from the surface side of the insulating film to the metal plate side can be reflected to the surface side by the insulating film.
  • the light emitted from the light emitting layer to the metal plate side is converted into a pigment on the element surface side by the insulating film.
  • the light of the corresponding wavelength can be reflected.
  • the thermosetting resin comprises a dicarboxylic acid-derived unit containing 90 mol% or more of terephthalic acid-derived units and isophthalic acid-derived units in total, and 90 mol of a polyol-derived unit having 2 to 5 carbon atoms. % Of the polyol-derived unit, and the molar percentage of the terephthalic acid-derived unit in the dicarboxylic acid-derived unit is 40 to 70%, and the isophthalic acid occupying in the dicarboxylic acid-derived unit. It contains a polyester resin in which the mole percentage of the acid-derived unit is 30 to 60%, and the adjusted average carbon number of the polyol-derived unit calculated by the above formula (1) is 3.4 or less.
  • polyester resin is a polymer substance having a large number of ester bonds formed by the condensation reaction of dicarboxylic acid and polyol, and the ester group constituting the ester bond is composed of only carbon atoms and oxygen atoms. Low affinity. Therefore, when an organic electronic device is produced using the insulating coating laminated metal plate of the present invention, even if water that adversely affects the organic electronic device enters the insulating coating containing the polyester resin, it is removed by drying. easy. For example, when an organic EL element is produced as an organic electronic device using the insulating film laminated metal plate of the present invention, it is possible to suppress the occurrence of dark spots (non-light emitting regions) due to water intrusion.
  • the total molar percentage of the terephthalic acid-derived unit and the isophthalic acid-derived unit in the dicarboxylic acid-derived unit is 90% or more.
  • Terephthalic acid which is a raw material for units derived from terephthalic acid
  • isophthalic acid which is a raw material for units derived from isophthalic acid
  • Terephthalic acid which is a raw material for units derived from terephthalic acid
  • isophthalic acid which is a raw material for units derived from isophthalic acid
  • the total molar percentage is preferably 100%.
  • the terephthalic acid-derived unit and the isophthalic acid-derived unit in the dicarboxylic acid-derived unit can be identified by, for example, a nuclear magnetic resonance method (NMR method).
  • the molar percentage of the terephthalic acid-derived units in the dicarboxylic acid-derived units is 40 to 70%.
  • the terephthalic acid-derived unit exhibits a structure that linearly extends the polyester resin, and is a structural unit that increases the hardness of the polyester resin by suppressing rotation of the polyester resin itself (rotation as a polyester resin molecule).
  • the molar percentage of the terephthalic acid-derived unit in the dicarboxylic acid-derived unit is 40% or more. Preferably it is 50% or more.
  • the molar percentage of the terephthalic acid-derived unit in the dicarboxylic acid-derived unit is 70% or less. Preferably it is 60% or less.
  • the molar percentage of the isophthalic acid-derived units in the dicarboxylic acid-derived units is 30 to 60%.
  • the unit derived from isophthalic acid is a structural unit that bends the polyester resin, facilitates the rotation of the polyester resin itself (rotation as a polyester resin molecule), and reduces the hardness of the polyester resin. Has the effect of softening.
  • the molar percentage of the units derived from isophthalic acid in the units derived from dicarboxylic acid is 30% or more. Preferably it is 40% or more.
  • the mole percentage of the isophthalic acid-derived unit in the dicarboxylic acid-derived unit is too high, the insulating film becomes too soft. Therefore, the molar percentage of the isophthalic acid-derived unit in the dicarboxylic acid-derived unit is 60% or less. Preferably it is 50% or less.
  • the mole percentage of the polyol-derived unit having 2 to 5 carbon atoms in the polyol-derived unit is 90% or more.
  • a polyol-derived unit having more than 5 carbon atoms is a structural unit that lowers the hardness of the polyester resin. If the molar percentage exceeds 10%, the insulating film does not satisfy the required hardness, and a conductive thin film layer is formed by sputtering. This is because wrinkles sometimes occur. From the viewpoint of stably ensuring the hardness of the polyester resin, the molar percentage of the polyol-derived unit having 2 to 5 carbon atoms in the polyol-derived unit is preferably 100%.
  • the polyol-derived unit having 2 to 5 carbon atoms in the polyol-derived unit can be identified by, for example, a nuclear magnetic resonance method.
  • the polyester resin is obtained by a condensation reaction between a dicarboxylic acid containing terephthalic acid and isophthalic acid and a polyol containing a polyol having 2 to 5 carbon atoms. Therefore, the dicarboxylic acid may contain a dicarboxylic acid other than terephthalic acid and isophthalic acid.
  • dicarboxylic acids examples include ⁇ , ⁇ -unsaturated dibasic acids such as maleic acid, fumaric acid, and itaconic acid, and orthophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, hexahydroisophthalic acid, hexa Hydroterephthalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, sebacic acid, 1,10-decanedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid And saturated dibasic acids excluding terephthalic acid and isophthalic acid such as 4,4'-biphenyldicarboxylic acid.
  • dibasic acids such as maleic acid, fumaric acid, and itaconic acid
  • orthophthalic acid tetrahydrophthalic acid
  • 2,6-naphthalenedicarboxylic acid 2,7-naphthalenedicarboxylic acid and 2,3-naphthalenedicarboxylic acid having a molecular structure similar to that of terephthalic acid and isophthalic acid.
  • the polyol may contain not only a polyol having 2 to 5 carbon atoms but also a polyol having 6 or more carbon atoms.
  • the polyol include ethylene glycols such as ethylene glycol, diethylene glycol, and polyethylene glycol, propylene glycols such as propylene glycol, dipropylene glycol, and polypropylene glycol, 2-methyl-1,3-propanediol, and 1,3-butane.
  • Diol adduct of bisphenol A and propylene oxide or ethylene oxide, glycerin, trimethylolpropane, 1,3-propanediol, 1,2-cyclohexane glycol, 1,3-cyclohexane glycol, 1,4-cyclohexane glycol, paraxylene Glycol, bicyclohexyl-4,4'-diol, 2,6-decalin glycol, tris (2-hydroxyethyl) isocyanurate, and the like. That. Only one kind of each of the polyol having 2 to 5 carbon atoms and the polyol having 6 or more carbon atoms may be used, or two or more kinds may be appropriately used in combination.
  • the polyol is preferably a diol, and the polyol having 2 to 5 carbon atoms is preferably a diol having 2 to 5 carbon atoms. More preferably, the polyol is only the polyol having 2 to 5 carbon atoms.
  • the diol having 2 carbon atoms include ethylene glycol.
  • the diol having 3 carbon atoms include 1,2-propanediol and 1,3-propanediol.
  • Examples of the diol having 4 carbon atoms include 2-methyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and 2,3-butanediol. Can do.
  • the diol having 5 carbon atoms include neopentyl glycol and 1,5-pentanediol.
  • the adjusted average carbon number of the polyol-derived unit calculated by the above formula (1) is 3.4 or less.
  • the adjusted average carbon number of the polyol-derived unit is an index that can adjust the hardness of the insulating film at a temperature of about 200 to 250 ° C., and was found by the present inventors in the process of reaching the present invention. is there.
  • the polyol-derived unit since the polyol-derived unit has a chain hydrocarbon as a skeleton, it has a property of making the polyester resin softer than the dicarboxylic acid-derived unit.
  • the adjusted average carbon number of the polyol-derived unit exceeds 3.4, the proportion of chain hydrocarbons in the polyester resin increases, resulting in a soft insulating film at a temperature of about 200 to 250 ° C. Wrinkles occur during the formation of the thin film layer. As the adjusted average carbon number of the polyol-derived unit is smaller, the generation of wrinkles during formation of the conductive thin film layer by sputtering is suppressed.
  • the adjusted average carbon number of the polyol-derived unit is preferably 3.2 or less, and more preferably 3.0 or less. However, since methanediol, which is a polyol having 1 carbon atom, is unstable, the practical lower limit of the adjusted average carbon number of the polyol-derived unit is 2.0.
  • the average carbon number of the polyol-derived unit refers to the sum of the values obtained by multiplying the carbon number of the individual polyol-derived unit constituting the polyol-derived unit by the molar ratio of the individual polyol-derived unit.
  • the polyol-derived unit A is composed of an individual polyol-derived unit A1 having a carbon number N1 with a mole percentage X1 mol% and an individual polyol-derived unit A2 with a carbon number N2 having a mole percentage X2 mol%
  • the average carbon number N of the unit A is calculated by (N1 ⁇ X1 + N2 ⁇ X2) / 100.
  • the carbon number of an individual polyol origin unit means the total carbon number contained in an individual polyol origin unit, and is the sum of carbon number of the main chain of an individual polyol origin unit, and carbon number of a side chain.
  • 2-Methyl-1,3-propanediol and 1,4-butanediol are polyols having the same total carbon number of 4 but different in main chain carbon number of 3 and 4. It has been confirmed by experiments by the present inventors that wrinkles generated during the formation of the conductive thin film layer are the same in an insulating film laminated metal plate produced using polyols containing these polyols individually.
  • thermosetting resin contains a crosslinking agent.
  • the insulating film not only exhibits thermosetting properties but also improves heat resistance.
  • transformation and alteration of an insulating film can be suppressed.
  • the crosslinking agent is not particularly limited as long as it is a substance capable of crosslinking the polyester resin, but a substance having good compatibility with the polyester resin and good liquid stability is preferable.
  • a crosslinking agent various commercially available products can be suitably used.
  • melamine type such as Nippon Poly
  • the content ratio of the polyester resin and the crosslinking agent in the thermosetting resin is not particularly limited, but the content ratio of the polyester resin is preferably 50% by mass or more.
  • white pigments include inorganic pigments such as titanium oxide, calcium carbonate, zinc oxide, barium sulfate, lithopone, and lead white, and organic pigments such as polyethylene, polystyrene, polyacrylate, urea resin, and melamine resin. Can be used. Among these, it is preferable to use titanium oxide exhibiting pure white color.
  • the insulating film contains a white pigment, the luminance of the organic EL element produced using the insulating film laminated metal plate of the present invention is improved.
  • black pigment for example, black: organic pigments such as aniline black and nigrosine, and inorganic pigments such as carbon black and iron black can be used.
  • the insulating film contains a black pigment, the darkness of the organic EL element produced using the insulating film laminated metal plate of the present invention when not emitting light is improved.
  • red pigment for example, organic pigments such as insoluble azo (naphthol and anilide) or soluble azo, and inorganic pigments such as bengara, cadmium red, and red lead can be used.
  • yellow pigments include organic pigments such as insoluble azo (naphthol and anilide), soluble azo, and quinacridone, and inorganic pigments such as chrome yellow, cadmium yellow, nickel titanium yellow, tan and strontium chromate Pigments can be used.
  • green pigment for example, an organic phthalocyanine pigment can be used.
  • blue pigments examples include inorganic pigments such as organic phthalocyanine pigments, dioxazine pigments, bitumen, ultramarine blue, cobalt blue, and emerald green.
  • organic pigment such as benzimidazolone or pyrazolone can be used as the orange color.
  • the preferable thickness of the insulating film is 10 to 50 ⁇ m.
  • the preferred thickness of the conductive thin film layer formed on the insulating coating is 0.01 to 1 ⁇ m as described later. is there.
  • the conductive thin film layer having a small thickness is easily affected by an insulating film having a large thickness, so that a quality defect is likely to occur. For example, if there is a defect such as a pinhole on the surface of the insulating film, water easily enters and dark spots are likely to appear.
  • the thickness of the conductive thin film layer formed on the convex part of the insulating film tends to be different from the thickness of the conductive thin film layer formed on the concave part of the insulating film. It tends to affect the quality and lifetime of the device.
  • the surface roughness in a 3 mm square region of the insulating film is preferably 10 nm or less, more preferably 5 nm or less, and further preferably 3 nm or less. Thereby, the wave
  • the surface roughness in a 3 mm square area can be measured by the measurement method described later.
  • CMP chemical mechanical polishing
  • the chemical mechanical polishing method is not particularly limited, and a known polishing method in which polishing is performed by the surface chemical action of the polishing agent itself or the action of chemical components contained in the polishing liquid may be used.
  • the abrasive is not particularly limited, and for example, silica, alumina, ceria, titania, zirconia, germania, or the like can be used.
  • the insulating film is preferably laminated by a coating method in which the composition for forming an insulating film is applied on the surface of the metal plate or on another layer. Therefore, it is desirable that the composition for forming an insulating film is liquid and includes a solvent. If the solvent used for the composition for insulating film preparations can melt
  • the solvent examples include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and ethylene glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; toluene, benzene, xylene, and solvesso Aromatic hydrocarbons such as (registered trademark) 100 (manufactured by ExxonMobil), Solvesso (registered trademark) 150 (manufactured by ExxonMobil); aliphatic hydrocarbons such as hexane, heptane, and octane; ethyl acetate, butyl acetate And the like; and the like.
  • the composition for insulating film preparation can adjust solid content, for example using the said solvent.
  • the coating method of the composition for forming an insulating film is not particularly limited, and a known method can be appropriately employed.
  • the coating method include a precoat method such as a bar coater method, a roll coater method, a curtain flow coater method, a spray method, and a spray ringer method.
  • the bar coater method, the roll coater method, the spray method, and the spray ringer method are preferable from the viewpoint of cost and the like.
  • the baking temperature is preferably 190 ° C. or higher and 250 ° C. or lower, and more preferably 200 ° C. or higher and 240 ° C. or lower when used in the precoat method.
  • the drying temperature is not limited as long as the insulating film is not deteriorated by heat.
  • the drying temperature is preferably about 190 to 250 ° C., more preferably about 200 to 240 ° C.
  • a reaching plate temperature may be used as the baking temperature and the drying temperature.
  • the manufacturing method of the polyester resin and the insulating coating laminated metal plate is, for example, as follows.
  • Antimony trioxide as a catalyst is added to the composition and heated at 180 to 210 ° C. under atmospheric pressure for 180 minutes to allow the condensation reaction to proceed. Subsequently, the temperature is raised to 250 ° C., the pressure is reduced to 1 to 5 mmHg, and then the condensation reaction is further advanced for 180 minutes and water generated by the condensation reaction is removed. Thereby, a polyester resin is obtained.
  • the polyol volatilizes, so the dicarboxylic acid-derived unit and the polyol-derived unit in the obtained polyester resin are approximately 1: 1 in molar ratio.
  • the exact charge amount of dicarboxylic acid and polyol is determined based on the molar ratio of the dicarboxylic acid-derived unit and the polyol-derived unit in the polyester resin obtained from the polyester resin-forming composition in which the content ratio of the dicarboxylic acid and the polyol is changed. .
  • a solution obtained by dissolving and dispersing the obtained polyester resin, a crosslinking agent, and a pigment added if necessary in a solvent is applied to a metal plate and heated. . Thereby, an insulating film is formed on the metal plate, and an insulating film laminated metal plate is obtained.
  • the solid content (polyester resin, crosslinking agent, pigment, etc.) is preferably 20 to 70% by mass. If the solid content is less than 20% by mass, the viscosity of the solution becomes too low, and it is necessary to repeat the coating several times until the target thickness of the insulating film is reached.
  • the pigment ratio in solid content is 60 mass% or less.
  • the viscosity of the solution becomes too high and coating itself becomes difficult.
  • the metal substrate of the present invention is obtained by laminating a conductive thin film layer on the insulating film of the insulating film laminated metal plate.
  • the conductive thin film layer is made of, for example, ZnO, ITO, or SnO 2 to which Al, B, Ga, Sb, or the like is added. Usually, it is made of ITO.
  • the layer structure of the conductive thin film layer may be a single layer structure or a laminated structure of two or more layers.
  • the material constituting each layer (that is, the above ZnO, ITO, or SnO 2 ) may be the same or different.
  • the thickness of the conductive thin film layer is not particularly limited, but is preferably 0.01 to 1 ⁇ m.
  • the surface roughness in a 3 mm square region of the conductive thin film layer is preferably 100 nm or less, more preferably 20 nm or less, still more preferably 10 nm or less, and even more preferably 5 nm or less. Thereby, a solar cell with high power generation efficiency and an organic EL element with high light emission illuminance can be produced.
  • the surface roughness in a 3 mm square region can be measured by the measurement method described later.
  • the conductive thin film layer has a heat resistance of about 200 ° C. or higher, an organic electronic device can be produced using the metal substrate of the present invention.
  • the conductive thin film layer functions as an anode. And since an electroconductive thin film layer has transparency, the light which the light emitting layer emitted to the metal plate side is reflected by the insulating film containing the pigment located under an electroconductive thin film layer.
  • Metal substrate manufacturing method Next, a method for manufacturing the metal substrate will be described.
  • the conductive thin film layer is formed by sputtering. More specifically, the insulating film laminated metal plate of the present invention is placed in a vacuum vessel, and a metal or metal oxide to be applied as a thin film is set as a target. For example, when an ITO layer is formed as the conductive thin film layer, a target made of ITO is used. Then, for example, a high voltage is applied to a rare gas element such as argon or nitrogen to make it collide with the target. Thereby, atoms and the like on the target surface are repelled, reach the insulating film laminated metal plate, and form a conductive thin film layer on the insulating film.
  • a rare gas element such as argon or nitrogen
  • the substrate type solar cell may have any known structure as long as it has the insulating film laminated metal plate of the present invention.
  • the substrate type solar cell basically has an insulating film laminated metal plate of the present invention on the insulating film.
  • the back electrode, the photoelectric conversion layer, and the front electrode are stacked in this order.
  • the photoelectric conversion layer is a layer that generates light by absorbing light that has passed through the transparent surface electrode, and both the back electrode and the surface electrode are for taking out the current generated in the photoelectric conversion layer. Both are made of a conductive material.
  • the surface electrode on the light incident side needs to have translucency. About a back surface electrode, a photoelectric converting layer, and a surface electrode, the material similar to a well-known substrate type thin film solar cell can be used.
  • the transparency of the insulating coating laminated metal plate is not required.
  • the top emission type organic EL element may have any known structure as long as it is provided with the insulating coating laminated metal plate of the present invention.
  • the insulating coating laminated metal plate of the present invention basically has an insulating coating.
  • the anode, the light emitting layer, and the cathode the same materials as known top emission thin film solar cells can be used.
  • a non-transparent metal plate can be used.
  • one aspect of the present invention includes a metal plate and an insulating film laminated on at least one surface side of the metal plate, the insulating film containing a thermosetting resin, and the heat
  • the curable resin comprises a dicarboxylic acid-derived unit containing 90 mol% or more of terephthalic acid-derived units and isophthalic acid-derived units in total, and a polyol-derived unit containing 90 mol% or more of a polyol-derived unit having 2 to 5 carbon atoms.
  • Containing a polyester resin wherein the molar percentage of the terephthalic acid-derived unit in the dicarboxylic acid-derived unit is 40 to 70%, and the molar percentage of the isophthalic acid-derived unit in the dicarboxylic acid-derived unit is 30 to A conductive thin film layer on the insulating film, wherein the adjusted average carbon number of the polyol-derived unit calculated by the above formula (1) is 60% or less.
  • the insulating film laminated metal plate of the present invention may further contain a pigment.
  • the organic EL element produced using the insulating coating laminated metal plate of the present invention reflects light having a wavelength corresponding to the pigment in the insulating coating to the element surface side. Can be improved.
  • the surface roughness in a 3 mm square region of the insulating coating is preferably 10 nm or less.
  • the surface of the insulating film becomes smooth within a practical range, and generation of dark spots can be suppressed.
  • a solar cell with high electric power generation efficiency and an organic EL element with high light emission illumination intensity can be produced.
  • Another aspect of the present invention is a metal substrate in which a conductive thin film layer is laminated on an insulating film of the insulating film laminated metal plate.
  • the organic EL element manufactured using the metal substrate of the present invention is less likely to cause uneven color and insufficient light emission illuminance, while the solar cell manufactured using the metal substrate of the present invention is The amount of power generation is difficult to decrease.
  • the surface roughness in a 3 mm square region of the conductive thin film layer is 100 nm or less. With this configuration, the surface of the conductive thin film layer becomes smooth within a practical range, and an organic EL element or a solar cell with stable quality and lifetime can be manufactured.
  • the metal substrate of the present invention can be used for a top emission type organic EL element or a substrate type thin film solar cell. With this configuration, a top emission type organic EL element with stable emission illuminance and a substrate type thin film solar cell with stable power generation can be manufactured.
  • an insulating film laminated metal plate capable of suppressing the generation of wrinkles when forming a conductive thin film layer by sputtering, and a metal substrate in which the generation of wrinkles on the surface of the conductive thin film layer is suppressed are provided. Can do.
  • composition ratio of each structural unit of the polyester resin 1 is such that the molar percentage of the terephthalic acid-derived unit in the dicarboxylic acid-derived unit is 50%, the molar percentage of the isophthalic acid-derived unit in the dicarboxylic acid-derived unit is 50%, and the polyol-derived unit.
  • the mole percentage of units derived from ethylene glycolic acid in 80% was 80%, and the mole percentage of units derived from neopentyl glycolic acid in units derived from polyol was 20%.
  • the average carbon number of the polyol-derived unit was calculated from the mole percentage of each derived unit in the polyol-derived unit obtained by NMR method and the carbon number of each derived unit. Then, the adjusted average carbon number of the polyol-derived unit was calculated from the average carbon number of the polyol-derived unit and the molar percentage of the terephthalic acid-derived unit in the dicarboxylic acid-derived unit. These calculation results are also shown in Table 1.
  • composition for insulating film preparation In a solvent in which xylene (boiling point: 140 ° C.) and cyclohexanone (boiling point: 156 ° C.) are mixed in equal amounts, 13.4 parts by weight of a polyester resin in terms of solids, 14.5 parts by weight of melamine resin (Super Becamine (registered trademark) J-820-60, manufactured by DIC Corporation) in terms of solids, titanium oxide particles ( 16.0 parts by mass in terms of solid content was added to Taipek (registered trademark) CR-50 (average particle size: 0.25 ⁇ m) manufactured by Ishihara Sangyo Co., Ltd., and finally, triethylenediamine manufactured by Tokyo Chemical Industry Co., Ltd. was added to 0.3 In addition to parts by mass, no. 1 was obtained. The amount of the mixed solvent of xylene and cyclohexanone was adjusted so that the total solid content of the polyester resin and melamine resin was 58% by mass.
  • [Surface polishing of insulating metal film] No. is attached to the holder to which the suction pad for mounting the substrate of the polishing apparatus is attached. 1 was set on a polishing pad attached to a surface plate of a polishing apparatus with the insulating film facing down.
  • abrasive alumina particles having a particle size of about 100 nm were used, the pressure was 65 gf / cm 2 , the rotational distance per revolution was 1 m, Chemical mechanical polishing was performed for 1 minute at each rotation speed of 50 rpm between the insulating film laminated metal plate 1 and the surface plate.
  • the surface of the insulating film was chemically mechanically polished.
  • the insulating film laminated metal plate 1 was washed by the following procedure. That is, no. 1 is first cleaned with ultrapure water, then ultrasonically cleaned with ultrapure water for 3 minutes at 23 kHz, and then ultrasonically cleaned with a detergent for removing organic substances at 23 kHz for 3 minutes. And then cleaning with ultrapure water, followed by ultrasonic cleaning with a detergent for removing ionic impurities at 43 kHz for 3 minutes, then cleaning with ultrapure water, and then ultrasonication with ultrapure water.
  • No. No. 1 of the metal substrate production conditions only the metal substrate is No. 1. No. 1 from No. 1 metal substrate. By changing to each of 2 to 9 metal substrates, No. 2 to 9 metal substrates were obtained.
  • Figure 2 shows No. It is an atomic force microscope image of the ITO layer surface in 1 metal substrate, and shows that there is no wrinkle on the ITO layer surface.
  • FIG. It is an atomic force microscope image of the ITO layer surface in 2 metal substrates, and shows that the ITO layer surface has wrinkles.
  • the unidirectional arithmetic mean roughness of a 10 ⁇ m square area is measured at five locations at the four corners and the center of the 3 mm square area using an atomic force microscope.
  • the thickness Ra1 and the arithmetic average roughness Ra2 in the direction perpendicular thereto are measured.
  • the average value of Ra1 and Ra2 be surface roughness Ra3 of a 10 micrometer square area
  • the average value of the surface roughness Ra3 of the five 10 ⁇ m square regions is defined as the surface roughness Ra ′ in the 3 mm square region.
  • Table 1 shows the measurement results.
  • the insulating film laminated metal plates 1 and 5 to 7 and the metal substrate are examples satisfying the conditions defined in the present invention. These showed that there was no wrinkle on the surface of the ITO layer and the surface roughness Ra ′ in a 3 mm square region was 100 nm or less.
  • the insulating film laminated metal plates and metal substrates of 2 to 4, 8, and 9 are examples that do not satisfy the condition “the adjusted average carbon number of the polyol-derived unit is 3.4 or less” defined in the present invention. These showed that the ITO layer surface had wrinkles and the surface roughness Ra 'in a 3 mm square region exceeded 100 nm.

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Abstract

The insulation film laminated metal plate of the present invention has a metal plate, and an insulation film laminated on at least one side of the metal plate, wherein: the insulation film contains a heat-curing resin; the heat-curing resin contains a polyester resin constituted by dicarboxylic acid-derived units containing at least 90 mol% in total of terephthalic acid-derived units and isophthalic acid-derived units, and polyol-derived units containing at least 90 mol% of polyol-derived units having a carbon number of 2 to 5; the mole percentage of the terephthalic acid-derived units in the dicarboxylic acid-derived units is 40–70% and the mole percentage of the isophthalic acid-derived units in the dicarboxylic acid-derived units is 30–60%; and the adjusted average carbon number of the polyol-derived units calculated using formula (1) is 3.4 or less.

Description

絶縁皮膜積層金属板及び金属基板Insulating film laminated metal plate and metal substrate
　本発明は、絶縁皮膜積層金属板及び金属基板に関する。より詳しくは、トップエミッション型有機ＥＬ素子又はサブストレート型薄膜太陽電池に用いられる絶縁皮膜積層金属板及び金属基板に関する。 The present invention relates to an insulating film laminated metal plate and a metal substrate. More specifically, the present invention relates to an insulating film laminated metal plate and a metal substrate used for a top emission type organic EL element or a substrate type thin film solar cell.
　有機半導体は、柔軟で薄型化でき、さらに省電力であるためトップエミッション型有機ＥＬ（エレクトロルミネッセンス）素子やサブストレート型薄膜太陽電池といった有機電子デバイスへの応用が期待されている。上記有機ＥＬ素子は、有機半導体を含む発光層を備えるとともに、例えば透明性と導電性を併せ持つＩＴＯ（酸化インジウムスズ）からなる陽極と例えばＩＺＯ（酸化インジウム亜鉛）からなる陰極とをさらに備える。一方、上記太陽電池は、有機半導体からなる光電変換層を備えるとともに、例えばそれぞれＩＴＯからなる裏面電極及び表面電極をさらに備える。 Organic semiconductors are flexible and can be made thin, and they are power-saving, so they are expected to be applied to organic electronic devices such as top emission type organic EL (electroluminescence) elements and substrate type thin film solar cells. The organic EL element includes a light emitting layer containing an organic semiconductor, and further includes an anode made of ITO (indium tin oxide) having both transparency and conductivity, and a cathode made of, for example, IZO (indium zinc oxide). On the other hand, the solar cell includes a photoelectric conversion layer made of an organic semiconductor, and further includes a back electrode and a front electrode made of ITO, for example.
　有機電子デバイスの基板として、ガラスを用いた場合には割れ易く加工性に乏しい問題があり、他方、プラスチックを用いた場合には透湿性があるためガスバリア層の設置が必要という問題がある。そのため、有機電子デバイスの基板として、絶縁皮膜を金属板上に積層した絶縁皮膜積層金属板の採用が検討されている。 When glass is used as a substrate of an organic electronic device, there is a problem that it is easily broken and poor in workability. On the other hand, when plastic is used, there is a problem that it is necessary to install a gas barrier layer because of moisture permeability. Therefore, the adoption of an insulating film laminated metal plate in which an insulating film is laminated on a metal plate has been studied as a substrate for organic electronic devices.
　例えば、特許文献１は、表面粗さが３０ｎｍ以下で膜厚が１０～４０μｍであるとともに熱硬化性樹脂としてポリエステルを含有する皮膜が１層のみ金属板の表面に積層された絶縁皮膜積層金属板を開示している。又、特許文献２は、金属板の片面又は両面に１層以上の熱硬化型樹脂塗膜層を備え、当該樹脂塗膜層は表面粗さが２０ｎｍ以下で総膜厚が１～３０μｍであるとともに主樹脂がポリエステル樹脂である絶縁皮膜積層金属板を開示している。 For example, Patent Document 1 discloses an insulating film laminated metal plate having a surface roughness of 30 nm or less, a film thickness of 10 to 40 μm, and a single film containing polyester as a thermosetting resin laminated on the surface of the metal plate. Is disclosed. Further, Patent Document 2 includes one or more thermosetting resin coating layers on one or both sides of a metal plate, and the resin coating layer has a surface roughness of 20 nm or less and a total film thickness of 1 to 30 μm. In addition, an insulating film laminated metal plate whose main resin is a polyester resin is disclosed.
　上記絶縁皮膜積層金属板の絶縁皮膜上に陽極、発光層及び陰極をこの順で積層することにより、上記有機ＥＬ素子が得られる。この有機ＥＬ素子を発光回路に設置して電流を流すことで、発光層が発光する。 The organic EL element is obtained by laminating the anode, the light emitting layer, and the cathode in this order on the insulating film of the insulating film laminated metal plate. When the organic EL element is installed in the light emitting circuit and a current is passed, the light emitting layer emits light.
　一方、上記絶縁皮膜積層金属板の絶縁皮膜上に裏面電極、光電変換層及び表面電極をこの順で積層することにより、上記太陽電池が得られる。この太陽電池を発電回路に設置して太陽光を照射することで、光電変換層で電荷の移動が生じて当該太陽電池が発電する。 On the other hand, the solar cell can be obtained by laminating the back electrode, the photoelectric conversion layer, and the front electrode in this order on the insulating film of the insulating film laminated metal plate. By installing this solar cell in a power generation circuit and irradiating sunlight, charge transfer occurs in the photoelectric conversion layer, and the solar cell generates power.
特開２０１４－２０８４７９号公報JP 2014-208479 A 特開２０１６－１９３５８０号公報Japanese Unexamined Patent Publication No. 2016-193580
　特許文献１及び特許文献２に開示された絶縁皮膜積層金属板を用いて上記有機ＥＬ素子を作製して発光させた場合には、当該有機ＥＬ素子は図１に示すように幅５～１０μｍで長さ２０～５０μｍの明暗の縞状模様を呈して発光することがある。このような縞状模様を呈して発光する有機ＥＬ素子は、発光層表面が均一に発光する有機ＥＬ素子と比べて、色むらや発光照度不足が生じ、有機ＥＬ素子としての要求性能を満たさない。後述の通り、上記縞状模様を呈した発光は、絶縁皮膜積層金属板が有する絶縁皮膜の上にスパッタリングによって導電性薄膜層が形成される際に、当該導電性薄膜層の表面に生じたしわに起因する。 When the organic EL element is fabricated using the insulating coating laminated metal plate disclosed in Patent Document 1 and Patent Document 2 to emit light, the organic EL element has a width of 5 to 10 μm as shown in FIG. It may emit light with a bright and dark striped pattern with a length of 20 to 50 μm. An organic EL element that emits light with such a striped pattern causes color unevenness and insufficient light emission illuminance as compared with an organic EL element that emits light uniformly on the surface of the light emitting layer, and does not satisfy the required performance as an organic EL element. . As described later, the light emission having the striped pattern is a wrinkle generated on the surface of the conductive thin film layer when the conductive thin film layer is formed on the insulating film of the insulating film laminated metal plate by sputtering. caused by.
　一方、特許文献１及び特許文献２に開示された絶縁皮膜積層金属板を用いて上記太陽電池を作製して発電させた場合には、導電性薄膜層の表面に生じたしわに起因して発電量が低下し得る。 On the other hand, when the solar cell is produced using the insulating coating laminated metal plate disclosed in Patent Document 1 and Patent Document 2 to generate electric power, power generation is caused by wrinkles generated on the surface of the conductive thin film layer. The amount can be reduced.
　そのため、導電性薄膜層の表面にしわが発生していない金属基板、及びスパッタリングによる導電性薄膜層形成時に当該しわが発生しない絶縁皮膜積層金属板が求められている。 Therefore, there is a demand for a metal substrate in which the surface of the conductive thin film layer is not wrinkled, and an insulating film laminated metal plate in which the wrinkle is not generated when the conductive thin film layer is formed by sputtering.
　本発明は上記事情に鑑みてなされたものであり、スパッタリングによる導電性薄膜層形成時にしわの発生を抑制することができる絶縁皮膜積層金属板、及び導電性薄膜層表面でのしわの発生が抑制された金属基板を提供することを目的とする。 The present invention has been made in view of the above circumstances, and it is possible to suppress the generation of wrinkles on the surface of the conductive thin film layer and the insulating film laminated metal plate capable of suppressing the generation of wrinkles when forming the conductive thin film layer by sputtering. An object of the present invention is to provide a finished metal substrate.
　本発明の一局面は、金属板と、当該金属板の少なくとも一方の面側に積層される絶縁皮膜とを有し、上記絶縁皮膜は熱硬化性樹脂を含有し、上記熱硬化性樹脂は、テレフタル酸由来単位及びイソフタル酸由来単位を合計で９０モル％以上含有するジカルボン酸由来単位と、炭素数２～５のポリオール由来単位を９０モル％以上含有するポリオール由来単位とから構成されるポリエステル樹脂を含有し、上記ジカルボン酸由来単位に占める上記テレフタル酸由来単位のモル百分率が４０～７０％であり、上記ジカルボン酸由来単位に占める上記イソフタル酸由来単位のモル百分率が３０～６０％であり、下記式（１）で算出されるポリオール由来単位の調整平均炭素数が３．４以下である、上記絶縁皮膜の上に導電性薄膜層を形成するための絶縁皮膜積層金属板である。 One aspect of the present invention has a metal plate and an insulating film laminated on at least one surface side of the metal plate, the insulating film contains a thermosetting resin, and the thermosetting resin is A polyester resin comprising a dicarboxylic acid-derived unit containing 90 mol% or more of terephthalic acid-derived units and isophthalic acid-derived units in total, and a polyol-derived unit containing 90 mol% or more of a polyol-derived unit having 2 to 5 carbon atoms. And the molar percentage of the terephthalic acid-derived unit in the dicarboxylic acid-derived unit is 40 to 70%, and the molar percentage of the isophthalic acid-derived unit in the dicarboxylic acid-derived unit is 30 to 60%, The adjusted average carbon number of the polyol-derived unit calculated by the following formula (1) is 3.4 or less, for forming a conductive thin film layer on the insulating film. A rim film laminated metal sheet.
Figure JPOXMLDOC01-appb-M000002
Figure JPOXMLDOC01-appb-M000002
　本発明の他の一局面は、上記絶縁皮膜積層金属板が有する絶縁皮膜の上に導電性薄膜層が積層された、金属基板である。 Another aspect of the present invention is a metal substrate in which a conductive thin film layer is laminated on an insulating film of the insulating film laminated metal plate.
　本発明の目的、特徴、局面及び利点は、以下の詳細な説明及び図面によって、より明白となる。 The objects, features, aspects and advantages of the present invention will become more apparent from the following detailed description and drawings.
図１は、従来の絶縁皮膜積層金属板を用いて作製されたトップエミッション型有機ＥＬ素子の表面における発光状態の光学顕微鏡像を示す図面代用写真である。FIG. 1 is a photo, which substitutes for a drawing, showing an optical microscope image of a light emission state on the surface of a top emission type organic EL device manufactured using a conventional insulating coating laminated metal plate. 図２は、実施例のＮｏ．１の金属基板におけるＩＴＯ層表面の原子間力顕微鏡像を示す図面代用写真である。FIG. 2 is a drawing-substituting photograph showing an atomic force microscope image of the surface of an ITO layer on one metal substrate. 図３は、実施例のＮｏ．２の金属基板におけるＩＴＯ層表面の原子間力顕微鏡像を示す図面代用写真である。FIG. 2 is a drawing-substituting photograph showing an atomic force microscope image of the surface of an ITO layer in a metal substrate of FIG.
　はじめに、本発明に到達した経緯の概要をトップエミッション型有機ＥＬ素子であるＯＬＥＤ素子（有機発光ダイオード素子）を作製した場合を例にして説明する。 First, an overview of how the present invention has been achieved will be described by taking as an example a case where an OLED element (organic light-emitting diode element), which is a top emission type organic EL element, is produced.
　金属板上に絶縁皮膜が積層された絶縁皮膜積層金属板を用いてＯＬＥＤ素子を作製する際、まず当該絶縁皮膜積層金属板を洗浄して、絶縁皮膜上に陽極であるＩＴＯ層をスパッタリングによって積層する。これにより、ＩＴＯ層を導電性薄膜層として有する金属基板が得られる。次に、ＩＴＯ層の上に正孔注入・輸送層、発光層及び電子輸送層をこの順で各層原料組成物を蒸着又は塗布及び加熱することにより積層する。続いて、電子輸送層の上に、陰極であるＩＺＯ層をスパッタリングによって形成する。そして、ＩＺＯ層の上に透明の封止ガラスを積層する。これにより、ＯＬＥＤ素子が得られる。上記正孔注入・輸送層、発光層及び電子輸送層を構成する有機半導体はいずれも電荷移動度が低いため、これら層の厚さはそれぞれ数十ｎｍから数百ｎｍまでの値に設定される。又、陰極を構成するＩＺＯ層の厚さも数十ｎｍから数百ｎｍまでの値に設定される。 When producing an OLED element using an insulating film laminated metal plate in which an insulating film is laminated on a metal plate, the insulating film laminated metal plate is first cleaned, and an ITO layer serving as an anode is laminated on the insulating film by sputtering. To do. Thereby, the metal substrate which has an ITO layer as an electroconductive thin film layer is obtained. Next, a hole injecting / transporting layer, a light emitting layer, and an electron transporting layer are laminated on the ITO layer by depositing or applying and heating each layer raw material composition in this order. Subsequently, an IZO layer as a cathode is formed on the electron transport layer by sputtering. Then, a transparent sealing glass is laminated on the IZO layer. Thereby, an OLED element is obtained. Since the organic semiconductors constituting the hole injection / transport layer, the light emitting layer, and the electron transport layer all have low charge mobility, the thicknesses of these layers are set to values of several tens to several hundreds of nanometers, respectively. . The thickness of the IZO layer constituting the cathode is also set to a value from several tens of nm to several hundreds of nm.
　このようにして得られたＯＬＥＤ素子を発光させたとき、色むらや発光照度不足が生じることがある。本発明者らは、色むらが生じたＯＬＥＤ素子の表面の発光状態を光学顕微鏡にて観察した。観察結果を図１に示す。図１は、当該色むらが生じたＯＬＥＤ素子の表面における発光状態の光学顕微鏡像を示す図面代用写真である。その結果、色むらは、ＯＬＥＤ素子が幅５～１０μｍで長さ２０～５０μｍの明暗の縞状模様を呈して発光することによって生じたことが判明した。又、このような縞状模様を呈して発光するＯＬＥＤ素子は、表面全体が均一に発光するＯＬＥＤ素子と比べて、発光照度が低いだけでなく、発光層中の強く発光する箇所の短寿命化に起因してＯＬＥＤ素子としての寿命が相対的に短くなり易いことも判明した。 When the OLED element obtained in this way is caused to emit light, color unevenness or light emission illuminance deficiency may occur. The present inventors observed the light emission state of the surface of the OLED element in which the color unevenness occurred with an optical microscope. The observation results are shown in FIG. FIG. 1 is a drawing-substituting photograph showing an optical microscope image of a light emission state on the surface of the OLED element in which the color unevenness occurs. As a result, it was found that the color unevenness was caused by the light emission of the OLED element having a light and dark stripe pattern having a width of 5 to 10 μm and a length of 20 to 50 μm. In addition, the OLED element that emits light with such a striped pattern has not only low emission illuminance, but also shortens the lifetime of the strongly emitting portion in the light emitting layer, compared with the OLED element that emits light uniformly over the entire surface. It has also been found that the lifetime as an OLED element tends to be relatively short due to the above.
　本発明者らは、色むらが生じたＯＬＥＤ素子が上記明暗の縞状模様を呈する原因を鋭意検討した。そして、その原因が、ＩＴＯ層の形成時に当該ＩＴＯ層の表面に数十ｎｍから数百ｎｍまでの高低差を有するしわが生じ、当該しわが、層厚の薄い正孔注入・輸送層、発光層、電子輸送層及びＩＺＯ層を介して、素子表面にまで反映されたためであることを突き止めた。 The inventors of the present invention diligently studied the cause of the OLED element in which the color unevenness is caused to exhibit the above-described bright and dark stripe pattern. And the cause is that when the ITO layer is formed, wrinkles having a height difference of several tens to several hundreds of nanometers occur on the surface of the ITO layer, and the wrinkles are thin hole injection / transport layers, light emission It was ascertained that it was reflected on the device surface through the layer, the electron transport layer, and the IZO layer.
　ＩＴＯ層表面の上記しわは、スパッタリングの熱影響を受けて、ＩＴＯ層の下方に位置する絶縁皮膜がエネルギー計算に基づいた推算値によれば約２００～２５０℃に温度上昇して当該絶縁皮膜が軟化して発生したと推察する。 The wrinkles on the surface of the ITO layer are affected by the heat of sputtering, and the insulating film located below the ITO layer rises to about 200 to 250 ° C. according to the estimated value based on the energy calculation. Presumed to have occurred due to softening.
　そこで、ＩＴＯ層形成時のスパッタリングによっても絶縁皮膜が２００～２５０℃程度の温度下で軟化しない方策を種々検討した。そして、絶縁皮膜が含有する熱硬化性樹脂に、特定組成のポリエステル樹脂を含有させることで、スパッタリングによって生じる絶縁皮膜の温度上昇に起因した軟化が抑制されて導電性薄膜層であるＩＴＯ層のしわ発生が抑制されることを見出し、本発明を完成させた。 Therefore, various measures were examined for preventing the insulating film from being softened at a temperature of about 200 to 250 ° C. even by sputtering during the formation of the ITO layer. Then, by adding a polyester resin having a specific composition to the thermosetting resin contained in the insulating film, the softening due to the temperature rise of the insulating film caused by sputtering is suppressed, and the wrinkle of the ITO layer which is the conductive thin film layer is suppressed. The inventors have found that generation is suppressed, and completed the present invention.
　尚、本明細書において、しわとは、被観察物の表層に形成された長さ２０～５０μｍで幅５～１０μｍで高さ（山と谷の高低差）１００ｎｍ以上の凸群（複数本の稜線）をいい、当該被観察物の表面を原子間力顕微鏡で観察したときに見られる凹凸をいう。しわの一例を図３に示す。図３は、実施例のＮｏ．２の金属基板におけるＩＴＯ層表面の原子間力顕微鏡像を示す図面代用写真である。 In this specification, a wrinkle is a convex group (a plurality of lines) having a length of 20 to 50 μm, a width of 5 to 10 μm and a height (height difference between peaks and valleys) of 100 nm or more formed on the surface layer of the object to be observed. (Ridge line), which refers to the unevenness observed when the surface of the object to be observed is observed with an atomic force microscope. An example of wrinkles is shown in FIG. FIG. 2 is a drawing-substituting photograph showing an atomic force microscope image of the surface of an ITO layer in a metal substrate of FIG.
　又、本明細書において、ジカルボン酸由来単位に占めるテレフタル酸由来単位のモル百分率とは、ジカルボン酸由来単位１００モル部に対するテレフタル酸由来単位のモル部の百分率をいう。 Moreover, in this specification, the molar percentage of the terephthalic acid-derived unit in the dicarboxylic acid-derived unit refers to the percentage of the molar part of the terephthalic acid-derived unit with respect to 100 mol part of the dicarboxylic acid-derived unit.
［絶縁皮膜積層金属板］
　次に、本発明の一局面である絶縁皮膜積層金属板について、説明する。 [Insulating film laminated metal plate]
Next, the insulating film laminated metal plate which is one aspect of the present invention will be described.
　本発明の絶縁皮膜積層金属板は、金属板と、当該金属板の少なくとも一方の面側に積層される絶縁皮膜とを有する。上記絶縁皮膜は熱硬化性樹脂を含有する。上記熱硬化性樹脂は、テレフタル酸由来単位及びイソフタル酸由来単位を合計で９０モル％以上含有するジカルボン酸由来単位と、炭素数２～５のポリオール由来単位を９０モル％以上含有するポリオール由来単位とから構成されるポリエステル樹脂を含有する。上記ジカルボン酸由来単位に占める上記テレフタル酸由来単位のモル百分率は４０～７０％である。上記ジカルボン酸由来単位に占める上記イソフタル酸由来単位のモル百分率は３０～６０％である。上記式（１）で算出されるポリオール由来単位の調整平均炭素数は３．４以下である。本発明の絶縁皮膜積層金属板は、上記絶縁皮膜の上に導電性薄膜層を形成するために用いられる。 The insulating film laminated metal plate of the present invention has a metal plate and an insulating film laminated on at least one surface side of the metal plate. The insulating film contains a thermosetting resin. The thermosetting resin includes a dicarboxylic acid-derived unit containing 90 mol% or more of terephthalic acid-derived units and isophthalic acid-derived units, and a polyol-derived unit containing 90 mol% or more of a polyol-derived unit having 2 to 5 carbon atoms. The polyester resin comprised from these is contained. The molar percentage of the terephthalic acid-derived unit in the dicarboxylic acid-derived unit is 40 to 70%. The mole percentage of the isophthalic acid-derived unit in the dicarboxylic acid-derived unit is 30 to 60%. The adjusted average carbon number of the polyol-derived unit calculated by the above formula (1) is 3.4 or less. The insulating film laminated metal plate of the present invention is used to form a conductive thin film layer on the insulating film.
　以下、このように規定した理由を説明する。 The following explains the reason for this provision.
１．金属板
　本発明の絶縁皮膜積層金属板に用いる金属板は、冷延鋼板、溶融純亜鉛めっき鋼板、合金化溶融Ｚｎ－Ｆｅめっき鋼板、合金化溶融Ｚｎ－５％Ａｌめっき鋼板、溶融５５％Ａｌ－Ｚｎ合金めっき鋼板、電気純亜鉛めっき鋼板、電気Ｚｎ－Ｎｉめっき鋼板、アルミニウム板、又はチタン板等である。当該金属板として、その表面に化学処理を施していない無処理材（いわゆる裸板）を用いることができる。しかし、金属板と絶縁皮膜の化学結合による密着性を向上させる観点から、当該金属板として、その表面にクロメート処理を施したクロメート材、或いは、その表面にノンクロメート処理を施したノンクロメート材を用いることが好ましい。環境保全の観点から、当該金属板としてノンクロメート材を用いることがより好ましい。当該金属板の厚みは特に限定されない。絶縁皮膜積層金属板の用途に応じて、例えば０．３～２．０ｍｍ程度である。 1. Metal plate The metal plate used for the insulating coating laminated metal plate of the present invention is a cold-rolled steel plate, a hot-dip galvanized steel plate, an alloyed hot-dip Zn-Fe-plated steel plate, an alloyed hot-melt Zn-5% Al-plated steel plate, a hot 55% Al -Zn alloy-plated steel sheet, electro-pure galvanized steel sheet, electro-Zn-Ni plated steel sheet, aluminum plate, titanium plate or the like. As the metal plate, an untreated material (so-called bare plate) whose surface is not chemically treated can be used. However, from the viewpoint of improving the adhesion due to the chemical bond between the metal plate and the insulating film, as the metal plate, a chromate material whose surface is subjected to chromate treatment or a non-chromate material whose surface is subjected to non-chromate treatment is used. It is preferable to use it. From the viewpoint of environmental conservation, it is more preferable to use a non-chromate material as the metal plate. The thickness of the metal plate is not particularly limited. The thickness is, for example, about 0.3 to 2.0 mm depending on the use of the insulating film laminated metal plate.
２．絶縁皮膜
　本発明では、絶縁皮膜は電気絶縁性を有する。より具体的には、本発明の絶縁皮膜積層金属板を用いて作製された有機電子デバイスの使用時において、絶縁皮膜はその直上に位置する層から金属板に電流が漏れない電気絶縁性を有する。 2. Insulating film In this invention, an insulating film has electrical insulation. More specifically, when an organic electronic device manufactured using the insulating film laminated metal plate of the present invention is used, the insulating film has an electrical insulation property that prevents current from leaking from the layer located immediately above the metal plate. .
　絶縁皮膜は、絶縁皮膜積層金属板の用途に応じて、金属板の片面側又は両面側に積層される。絶縁皮膜は、金属板の直上に積層されてもよいし、他の層を介して金属板に積層されてもよい。金属板に絶縁皮膜を積層することにより、金属板と絶縁皮膜の上層側に積層される層（例えば、導電性薄膜層）との間の電気絶縁性が確保される。 The insulating film is laminated on one side or both sides of the metal plate depending on the application of the insulating film laminated metal plate. The insulating film may be laminated directly on the metal plate, or may be laminated on the metal plate via another layer. By laminating the insulating film on the metal plate, electrical insulation between the metal plate and a layer (for example, a conductive thin film layer) laminated on the upper side of the insulating film is ensured.
　絶縁皮膜の厚さは特に限定されないが、絶縁皮膜の電気絶縁性を安定的に確保する観点から、絶縁皮膜の厚さは１０μｍ以上であることが好ましい。一方、絶縁皮膜の厚さが５０μｍを超えた場合には、絶縁皮膜の電気絶縁性が飽和する傾向を示すので、絶縁皮膜の厚さは５０μｍ以下であることが好ましい。 The thickness of the insulating film is not particularly limited, but it is preferable that the thickness of the insulating film is 10 μm or more from the viewpoint of stably ensuring the electrical insulation of the insulating film. On the other hand, when the thickness of the insulating film exceeds 50 μm, the electric insulating property of the insulating film tends to be saturated, and therefore the thickness of the insulating film is preferably 50 μm or less.
　絶縁皮膜は熱硬化性樹脂を主体的に含有する。 The insulating film mainly contains a thermosetting resin.
　又、絶縁皮膜は、絶縁皮膜積層金属板の用途に応じて、当該絶縁皮膜積層金属板を用いて作製された有機電子デバイスの発光色を調整するために、後述するように、例えば、酸化チタン等の白色顔料、カーボンブラック等の黒色顔料等のいろいろな色の顔料を一種又は二種以上含有してもよい。絶縁皮膜が顔料を含有することで、絶縁皮膜の表面側から金属板側に透過する光のうち、特定波長の光を絶縁皮膜にて表面側に反射させることができる。例えば、本発明の絶縁皮膜積層金属板を用いてＯＬＥＤ素子を作製し、当該ＯＬＥＤ素子を発光させた場合、発光層から金属板側に発した光は、絶縁皮膜にて素子表面側に顔料に対応した波長の光を反射させることができる。 In addition, the insulating film is formed of, for example, titanium oxide as described later in order to adjust the light emission color of an organic electronic device produced using the insulating film laminated metal plate according to the use of the insulating film laminated metal plate. 1 type or 2 or more types of pigments of various colors, such as white pigments, such as carbon black, and black pigments, such as carbon black, may be contained. When the insulating film contains a pigment, light having a specific wavelength among the light transmitted from the surface side of the insulating film to the metal plate side can be reflected to the surface side by the insulating film. For example, when an OLED element is produced using the insulating film laminated metal plate of the present invention and the OLED element emits light, the light emitted from the light emitting layer to the metal plate side is converted into a pigment on the element surface side by the insulating film. The light of the corresponding wavelength can be reflected.
２－１．熱硬化性樹脂
　本発明では、熱硬化性樹脂は、テレフタル酸由来単位及びイソフタル酸由来単位を合計で９０モル％以上含有するジカルボン酸由来単位と、炭素数２～５のポリオール由来単位を９０モル％以上含有するポリオール由来単位とから構成されるポリエステル樹脂であって、上記ジカルボン酸由来単位に占める上記テレフタル酸由来単位のモル百分率が４０～７０％であり、上記ジカルボン酸由来単位に占める上記イソフタル酸由来単位のモル百分率が３０～６０％であり、上記式（１）で算出されるポリオール由来単位の調整平均炭素数が３．４以下であるポリエステル樹脂を含有する。 2-1. Thermosetting resin In the present invention, the thermosetting resin comprises a dicarboxylic acid-derived unit containing 90 mol% or more of terephthalic acid-derived units and isophthalic acid-derived units in total, and 90 mol of a polyol-derived unit having 2 to 5 carbon atoms. % Of the polyol-derived unit, and the molar percentage of the terephthalic acid-derived unit in the dicarboxylic acid-derived unit is 40 to 70%, and the isophthalic acid occupying in the dicarboxylic acid-derived unit. It contains a polyester resin in which the mole percentage of the acid-derived unit is 30 to 60%, and the adjusted average carbon number of the polyol-derived unit calculated by the above formula (1) is 3.4 or less.
２－１－１．ポリエステル樹脂
　上記ポリエステル樹脂は、ジカルボン酸とポリオールの縮合反応によって形成されるエステル結合を多数有する高分子物質であり、エステル結合を構成するエステル基は炭素原子と酸素原子のみからなるので、水との親和性が低い。そのため、本発明の絶縁皮膜積層金属板を用いて有機電子デバイスを作製する際、当該有機電子デバイスに悪影響を及ぼす水が上記ポリエステル樹脂を含有する絶縁皮膜内部に浸入したとしても、乾燥により除去され易い。例えば、本発明の絶縁皮膜積層金属板を用いて有機電子デバイスとして有機ＥＬ素子を作製した場合には、水の浸入に起因するダークスポット（非発光領域）の発生を抑制することができる。 2-1-1. Polyester resin The polyester resin is a polymer substance having a large number of ester bonds formed by the condensation reaction of dicarboxylic acid and polyol, and the ester group constituting the ester bond is composed of only carbon atoms and oxygen atoms. Low affinity. Therefore, when an organic electronic device is produced using the insulating coating laminated metal plate of the present invention, even if water that adversely affects the organic electronic device enters the insulating coating containing the polyester resin, it is removed by drying. easy. For example, when an organic EL element is produced as an organic electronic device using the insulating film laminated metal plate of the present invention, it is possible to suppress the occurrence of dark spots (non-light emitting regions) due to water intrusion.
　上記ポリエステル樹脂において、ジカルボン酸由来単位に占めるテレフタル酸由来単位及びイソフタル酸由来単位の合計モル百分率は９０％以上である。テレフタル酸由来単位の原料であるテレフタル酸及びイソフタル酸由来単位の原料であるイソフタル酸は、芳香族ジカルボン酸であり、熱的安定性に優れる。そして、これらは他の芳香族ジカルボンよりも安価である。このため、上記合計モル百分率を９０％以上にすることにより、相対的に低コストでありながら耐熱性を確保して、スパッタリングによる導電性薄膜層形成時にしわの発生を抑制することができる。製造コストを抑制する観点から、上記合計モル百分率は１００％であることが好ましい。ジカルボン酸由来単位におけるテレフタル酸由来単位及びイソフタル酸由来単位は、例えば、核磁気共鳴法（ＮＭＲ法）により同定することができる。 In the polyester resin, the total molar percentage of the terephthalic acid-derived unit and the isophthalic acid-derived unit in the dicarboxylic acid-derived unit is 90% or more. Terephthalic acid, which is a raw material for units derived from terephthalic acid, and isophthalic acid, which is a raw material for units derived from isophthalic acid, are aromatic dicarboxylic acids and have excellent thermal stability. And they are cheaper than other aromatic dicarboxylic acids. For this reason, by setting the total mole percentage to 90% or more, heat resistance can be ensured at a relatively low cost, and generation of wrinkles can be suppressed when forming a conductive thin film layer by sputtering. From the viewpoint of suppressing the manufacturing cost, the total molar percentage is preferably 100%. The terephthalic acid-derived unit and the isophthalic acid-derived unit in the dicarboxylic acid-derived unit can be identified by, for example, a nuclear magnetic resonance method (NMR method).
　上記ポリエステル樹脂において、ジカルボン酸由来単位に占めるテレフタル酸由来単位のモル百分率は４０～７０％である。テレフタル酸由来単位は上記ポリエステル樹脂を直線的に伸長させる構造を呈し、上記ポリエステル樹脂自体の回転（ポリエステル樹脂分子としての回転）を抑制して上記ポリエステル樹脂の硬さを高める構成単位であり、ひいては絶縁皮膜の硬さを高める作用を有する。絶縁皮膜の硬さを確保する観点から、ジカルボン酸由来単位に占めるテレフタル酸由来単位のモル百分率は４０％以上とする。好ましくは５０％以上である。一方、ジカルボン酸由来単位に占めるテレフタル酸由来単位のモル百分率が高過ぎると、絶縁皮膜が硬くなり過ぎて絶縁皮膜積層金属板の加工性が低下する。そのため、ジカルボン酸由来単位に占めるテレフタル酸由来単位のモル百分率は７０％以下とする。好ましくは６０％以下である。 In the above polyester resin, the molar percentage of the terephthalic acid-derived units in the dicarboxylic acid-derived units is 40 to 70%. The terephthalic acid-derived unit exhibits a structure that linearly extends the polyester resin, and is a structural unit that increases the hardness of the polyester resin by suppressing rotation of the polyester resin itself (rotation as a polyester resin molecule). Has the effect of increasing the hardness of the insulating film. From the viewpoint of ensuring the hardness of the insulating film, the molar percentage of the terephthalic acid-derived unit in the dicarboxylic acid-derived unit is 40% or more. Preferably it is 50% or more. On the other hand, when the molar percentage of the terephthalic acid-derived unit in the dicarboxylic acid-derived unit is too high, the insulating film becomes too hard and the workability of the insulating film-laminated metal plate is lowered. Therefore, the molar percentage of the terephthalic acid-derived unit in the dicarboxylic acid-derived unit is 70% or less. Preferably it is 60% or less.
　上記ポリエステル樹脂において、ジカルボン酸由来単位に占めるイソフタル酸由来単位のモル百分率は３０～６０％である。イソフタル酸由来単位は上記ポリエステル樹脂を屈曲させる構造を呈し、上記ポリエステル樹脂自体の回転（ポリエステル樹脂分子としての回転）を容易にして上記ポリエステル樹脂の硬さを低める構成単位であり、ひいては絶縁皮膜を柔らかくする作用を有する。絶縁皮膜の柔らかさを確保する観点から、ジカルボン酸由来単位に占めるイソフタル酸由来単位のモル百分率は３０％以上とする。好ましくは４０％以上である。一方、ジカルボン酸由来単位に占めるイソフタル酸由来単位のモル百分率が高過ぎると、絶縁皮膜が柔らかくなり過ぎる。そのため、ジカルボン酸由来単位に占めるイソフタル酸由来単位のモル百分率は６０％以下とする。好ましくは５０％以下である。 In the above polyester resin, the molar percentage of the isophthalic acid-derived units in the dicarboxylic acid-derived units is 30 to 60%. The unit derived from isophthalic acid is a structural unit that bends the polyester resin, facilitates the rotation of the polyester resin itself (rotation as a polyester resin molecule), and reduces the hardness of the polyester resin. Has the effect of softening. From the viewpoint of ensuring the softness of the insulating film, the molar percentage of the units derived from isophthalic acid in the units derived from dicarboxylic acid is 30% or more. Preferably it is 40% or more. On the other hand, when the mole percentage of the isophthalic acid-derived unit in the dicarboxylic acid-derived unit is too high, the insulating film becomes too soft. Therefore, the molar percentage of the isophthalic acid-derived unit in the dicarboxylic acid-derived unit is 60% or less. Preferably it is 50% or less.
　上記ポリエステル樹脂において、ポリオール由来単位に占める炭素数２～５のポリオール由来単位のモル百分率は９０％以上である。炭素数５を超えるポリオール由来単位は上記ポリエステル樹脂の硬さを低める構成単位であり、そのモル百分率が１０％を超えると絶縁皮膜は要求された硬さを満たさなくなり、スパッタリングによる導電性薄膜層形成時にしわが発生するからである。上記ポリエステル樹脂の硬さを安定的に確保する観点から、ポリオール由来単位に占める炭素数２～５のポリオール由来単位のモル百分率は１００％であることが好ましい。ポリオール由来単位における炭素数２～５のポリオール由来単位は、例えば、核磁気共鳴法により同定することができる。 In the above polyester resin, the mole percentage of the polyol-derived unit having 2 to 5 carbon atoms in the polyol-derived unit is 90% or more. A polyol-derived unit having more than 5 carbon atoms is a structural unit that lowers the hardness of the polyester resin. If the molar percentage exceeds 10%, the insulating film does not satisfy the required hardness, and a conductive thin film layer is formed by sputtering. This is because wrinkles sometimes occur. From the viewpoint of stably ensuring the hardness of the polyester resin, the molar percentage of the polyol-derived unit having 2 to 5 carbon atoms in the polyol-derived unit is preferably 100%. The polyol-derived unit having 2 to 5 carbon atoms in the polyol-derived unit can be identified by, for example, a nuclear magnetic resonance method.
　上記ポリエステル樹脂は、テレフタル酸及びイソフタル酸を含有するジカルボン酸と、炭素数２～５のポリオールを含有するポリオールとの縮合反応で得られる。そのため、上記ジカルボン酸はテレフタル酸及びイソフタル酸以外のジカルボン酸を含有してもよい。このようなジカルボン酸として、例えば、マレイン酸、フマル酸、イタコン酸等のα，β－不飽和二塩基酸や、例えば、オルトフタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、ヘキサヒドロイソフタル酸、ヘキサヒドロテレフタル酸、コハク酸、マロン酸、グルタル酸、アジピン酸、セバシン酸、１，１０－デカンジカルボン酸、２，６－ナフタレンジカルボン酸、２，７－ナフタレンジカルボン酸、２，３－ナフタレンジカルボン酸、４，４′－ビフェニルジカルボン酸等のテレフタル酸及びイソフタル酸を除いた飽和二塩基酸を挙げることができる。このうち、テレフタル酸及びイソフタル酸と分子構造が似ている２，６－ナフタレンジカルボン酸、２，７－ナフタレンジカルボン酸及び２，３－ナフタレンジカルボン酸の一種又は二種以上を用いることが好ましい。 The polyester resin is obtained by a condensation reaction between a dicarboxylic acid containing terephthalic acid and isophthalic acid and a polyol containing a polyol having 2 to 5 carbon atoms. Therefore, the dicarboxylic acid may contain a dicarboxylic acid other than terephthalic acid and isophthalic acid. Examples of such dicarboxylic acids include α, β-unsaturated dibasic acids such as maleic acid, fumaric acid, and itaconic acid, and orthophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, hexahydroisophthalic acid, hexa Hydroterephthalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, sebacic acid, 1,10-decanedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid And saturated dibasic acids excluding terephthalic acid and isophthalic acid such as 4,4'-biphenyldicarboxylic acid. Among these, it is preferable to use one or more of 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid and 2,3-naphthalenedicarboxylic acid having a molecular structure similar to that of terephthalic acid and isophthalic acid.
　一方、上記ポリオールは炭素数２～５のポリオールを含有するだけでなく、炭素数６以上のポリオールを含有してもよい。上記ポリオールとして、例えば、エチレングリコール、ジエチレングリコール、ポリエチレングリコール等のエチレングリコール類、プロピレングリコール、ジプロピレングリコール、ポリプロピレングリコール等のプロピレングリコール類、２－メチル－１，３－プロパンジオール、１，３－ブタンジオール、ビスフェノールＡとプロピレンオキシド又はエチレンオキシドとの付加物、グリセリン、トリメチロールプロパン、１，３－プロパンジオール、１，２－シクロヘキサングリコール、１，３－シクロヘキサングリコール、１，４－シクロヘキサングリコール、パラキシレングリコール、ビシクロヘキシル－４，４′－ジオール、２，６－デカリングリコール、トリス（２－ヒドロキシエチル）イソシアヌレート等を挙げることができる。炭素数２～５のポリオール及び炭素数６以上のポリオールは、それぞれ一種類のみを用いてもよいし、適宜、二種類以上を組合せて用いてもよい。 On the other hand, the polyol may contain not only a polyol having 2 to 5 carbon atoms but also a polyol having 6 or more carbon atoms. Examples of the polyol include ethylene glycols such as ethylene glycol, diethylene glycol, and polyethylene glycol, propylene glycols such as propylene glycol, dipropylene glycol, and polypropylene glycol, 2-methyl-1,3-propanediol, and 1,3-butane. Diol, adduct of bisphenol A and propylene oxide or ethylene oxide, glycerin, trimethylolpropane, 1,3-propanediol, 1,2-cyclohexane glycol, 1,3-cyclohexane glycol, 1,4-cyclohexane glycol, paraxylene Glycol, bicyclohexyl-4,4'-diol, 2,6-decalin glycol, tris (2-hydroxyethyl) isocyanurate, and the like. That. Only one kind of each of the polyol having 2 to 5 carbon atoms and the polyol having 6 or more carbon atoms may be used, or two or more kinds may be appropriately used in combination.
　上記ポリオールはジオールであることが好ましく、上記炭素数２～５のポリオールは炭素数２～５のジオールであることが好ましい。そして、上記ポリオールは上記炭素数２～５のポリオールのみであることがより好ましい。炭素数２のジオールとして、例えば、エチレングリコールを挙げることができる。炭素数３のジオールとして、例えば、１，２－プロパンジオール、１，３－プロパンジオールを挙げることができる。炭素数４のジオールとして、例えば、２－メチル－１，３－プロパンジオール、１，２－ブタンジオール、１，３－ブタンジオール、１，４－ブタンジオール、２，３－ブタンジオールを挙げることができる。炭素数５のジオールとして、例えば、ネオペンチルグリコール、１，５－ペンタンジオールを挙げることができる。 The polyol is preferably a diol, and the polyol having 2 to 5 carbon atoms is preferably a diol having 2 to 5 carbon atoms. More preferably, the polyol is only the polyol having 2 to 5 carbon atoms. Examples of the diol having 2 carbon atoms include ethylene glycol. Examples of the diol having 3 carbon atoms include 1,2-propanediol and 1,3-propanediol. Examples of the diol having 4 carbon atoms include 2-methyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and 2,3-butanediol. Can do. Examples of the diol having 5 carbon atoms include neopentyl glycol and 1,5-pentanediol.
　上記ポリエステル樹脂において、上記式（１）で算出されるポリオール由来単位の調整平均炭素数は３．４以下である。ポリオール由来単位の調整平均炭素数は、絶縁皮膜の２００～２５０℃程度の温度下における硬さを調整することができる指標であり、本発明者らが本発明に到達する過程で見出したものである。上記ポリエステル樹脂において、上記ポリオール由来単位は鎖状炭化水素を骨格とするため、上記ジカルボン酸由来単位と比べて上記ポリエステル樹脂を柔らかくする性質を有する。ポリオール由来単位の調整平均炭素数が３．４を超えると、上記ポリエステル樹脂中の鎖状炭化水素の割合が大きくなる結果、２００～２５０℃程度の温度において絶縁皮膜が柔らかくなり、スパッタリングによる導電性薄膜層形成時にしわが発生する。ポリオール由来単位の調整平均炭素数が小さい程、スパッタリングによる導電性薄膜層形成時のしわ発生が抑制される。ポリオール由来単位の調整平均炭素数は、３．２以下であることが好ましく、３．０以下であることがより好ましい。但し、炭素数１のポリオールであるメタンジオールは不安定であるため、ポリオール由来単位の調整平均炭素数の実質的な下限値は２．０である。 In the polyester resin, the adjusted average carbon number of the polyol-derived unit calculated by the above formula (1) is 3.4 or less. The adjusted average carbon number of the polyol-derived unit is an index that can adjust the hardness of the insulating film at a temperature of about 200 to 250 ° C., and was found by the present inventors in the process of reaching the present invention. is there. In the polyester resin, since the polyol-derived unit has a chain hydrocarbon as a skeleton, it has a property of making the polyester resin softer than the dicarboxylic acid-derived unit. If the adjusted average carbon number of the polyol-derived unit exceeds 3.4, the proportion of chain hydrocarbons in the polyester resin increases, resulting in a soft insulating film at a temperature of about 200 to 250 ° C. Wrinkles occur during the formation of the thin film layer. As the adjusted average carbon number of the polyol-derived unit is smaller, the generation of wrinkles during formation of the conductive thin film layer by sputtering is suppressed. The adjusted average carbon number of the polyol-derived unit is preferably 3.2 or less, and more preferably 3.0 or less. However, since methanediol, which is a polyol having 1 carbon atom, is unstable, the practical lower limit of the adjusted average carbon number of the polyol-derived unit is 2.0.
　上記式（１）中のポリオール由来単位の平均炭素数とは、ポリオール由来単位を構成する個別ポリオール由来単位の炭素数に当該個別ポリオール由来単位のモル割合を掛けた値の総和をいう。例えば、ポリオール由来単位Ａがモル百分率Ｘ１モル％である炭素数Ｎ１の個別ポリオール由来単位Ａ１とモル百分率がＸ２モル％である炭素数Ｎ２の個別ポリオール由来単位Ａ２とによって構成される場合、ポリオール由来単位Ａの平均炭素数Ｎは、（Ｎ１×Ｘ１＋Ｎ２×Ｘ２）／１００で算出される。そして、個別ポリオール由来単位の炭素数とは、個別ポリオール由来単位に含まれる全炭素数をいい、個別ポリオール由来単位の主鎖の炭素数と側鎖の炭素数の和である。 In the above formula (1), the average carbon number of the polyol-derived unit refers to the sum of the values obtained by multiplying the carbon number of the individual polyol-derived unit constituting the polyol-derived unit by the molar ratio of the individual polyol-derived unit. For example, when the polyol-derived unit A is composed of an individual polyol-derived unit A1 having a carbon number N1 with a mole percentage X1 mol% and an individual polyol-derived unit A2 with a carbon number N2 having a mole percentage X2 mol%, the polyol is derived. The average carbon number N of the unit A is calculated by (N1 × X1 + N2 × X2) / 100. And the carbon number of an individual polyol origin unit means the total carbon number contained in an individual polyol origin unit, and is the sum of carbon number of the main chain of an individual polyol origin unit, and carbon number of a side chain.
　２－メチル－１，３－プロパンジオールと１，４－ブタンジオールは、全炭素数がいずれも４で同一であるものの、主鎖の炭素数が３と４で相違するポリオールである。これらポリオールをそれぞれ個別に含有するポリオールを用いて作製された絶縁皮膜積層金属板では、導電性薄膜層形成時に発生したしわが同程度であることが、本発明者らの実験によって確認された。 2-Methyl-1,3-propanediol and 1,4-butanediol are polyols having the same total carbon number of 4 but different in main chain carbon number of 3 and 4. It has been confirmed by experiments by the present inventors that wrinkles generated during the formation of the conductive thin film layer are the same in an insulating film laminated metal plate produced using polyols containing these polyols individually.
２－１－２．架橋剤
　本発明では、熱硬化性樹脂は架橋剤を含有する。これにより、絶縁皮膜は熱硬化性を示すだけでなく、耐熱性も向上する。そして、本発明の絶縁皮膜積層金属板を用いて有機電子デバイスを作製する際、絶縁皮膜の変形や変質を抑制することができる。 2-1-2. Crosslinking agent In the present invention, the thermosetting resin contains a crosslinking agent. Thereby, the insulating film not only exhibits thermosetting properties but also improves heat resistance. And when producing an organic electronic device using the insulating-film laminated metal plate of this invention, a deformation | transformation and alteration of an insulating film can be suppressed.
　架橋剤は、上記ポリエステル樹脂を架橋できる物質であれば特に限定されないが、上記ポリエステル樹脂との相溶性がよく、液安定性のよい物質が好ましい。このような架橋剤としては、種々の市販品を好適に用いることができる。例えば、イソシアネート系では、ミリオネート（登録商標）Ｎ、コロネート（登録商標）Ｔ、コロネート（登録商標）ＨＬ、コロネート（登録商標）２０３０、スプラセック（登録商標）３３４０、ダルトセック１３５０、ダルトセック２１７０、ダルトセック２２８０（以上、日本ポリウレタン工業株式会社製）等、メラミン系では、ニカラック（登録商標）ＭＳ－１１、ニカラック（登録商標）ＭＳ２１（以上、株式会社三和ケミカル製）、スーパーベッカミン（登録商標）Ｌ－１０５－６０、スーパーベッカミン（登録商標）Ｊ－８２０－６０（以上、ＤＩＣ株式会社製）、エポキシ系では、ハードナーＨＹ９５１、ハードナーＨＹ９５７（以上、ＢＡＳＦ製）、スミキュアーＤＴＡ、スミキュアーＴＴＡ（以上、住友化学株式会社製）等を挙げることができる。 The crosslinking agent is not particularly limited as long as it is a substance capable of crosslinking the polyester resin, but a substance having good compatibility with the polyester resin and good liquid stability is preferable. As such a crosslinking agent, various commercially available products can be suitably used. For example, in the isocyanate system, Millionate (registered trademark) N, Coronate (registered trademark) T, Coronate (registered trademark) HL, Coronate (registered trademark) 2030, Suprasec (registered trademark) 3340, Daltsec 1350, Daltsec 2170, Daltsec 2280 ( As described above, for melamine type such as Nippon Polyurethane Industry Co., Ltd., Nicarak (registered trademark) MS-11, Nicarac (registered trademark) MS21 (manufactured by Sanwa Chemical Co., Ltd.), Super Becamine (registered trademark) L- 105-60, Super Becamine (registered trademark) J-820-60 (above, manufactured by DIC Corporation), Epoxy, Hardener HY951, Hardener HY957 (above, manufactured by BASF), SumiCure DTA, SumiCure TTA (above, Sumitomo) Made by Chemical Co., Ltd. And the like can be given.
　熱硬化性樹脂における上記ポリエステル樹脂及び上記架橋剤の含有比率はそれぞれ特に制限されないが、ポリエステル樹脂の含有比率は５０質量％以上であることが好ましい。 The content ratio of the polyester resin and the crosslinking agent in the thermosetting resin is not particularly limited, but the content ratio of the polyester resin is preferably 50% by mass or more.
２－２．顔料
　白色顔料として、例えば、酸化チタン、炭酸カルシウム、酸化亜鉛、硫酸バリウム、リトポン、鉛白等の無機系顔料や、例えば、ポリエチレン、ポリスチレン、ポリアクリレート、尿素樹脂、メラミン樹脂等の有機系顔料を用いることができる。これらの中で、純白色を呈する酸化チタンを用いることが好ましい。絶縁皮膜が白色顔料を含有することにより、本発明の絶縁皮膜積層金属板を用いて作製された有機ＥＬ素子の輝度が向上する。 2-2. Pigments Examples of white pigments include inorganic pigments such as titanium oxide, calcium carbonate, zinc oxide, barium sulfate, lithopone, and lead white, and organic pigments such as polyethylene, polystyrene, polyacrylate, urea resin, and melamine resin. Can be used. Among these, it is preferable to use titanium oxide exhibiting pure white color. When the insulating film contains a white pigment, the luminance of the organic EL element produced using the insulating film laminated metal plate of the present invention is improved.
　黒色顔料として、例えば、黒色：アニリンブラック、ニグロシン等の有機系顔料や、例えば、カーボンブラック、鉄黒等の無機系顔料を用いることができる。絶縁皮膜が黒色顔料を含有することにより、本発明の絶縁皮膜積層金属板を用いて作製された有機ＥＬ素子の非発光時の暗度が向上する。 As the black pigment, for example, black: organic pigments such as aniline black and nigrosine, and inorganic pigments such as carbon black and iron black can be used. When the insulating film contains a black pigment, the darkness of the organic EL element produced using the insulating film laminated metal plate of the present invention when not emitting light is improved.
　赤色顔料として、例えば、不溶性アゾ系（ナフトール系及びアニライド系）又は溶性アゾ系等の有機系顔料や、例えば、べんがら、カドミウムレッド、鉛丹等の無機系顔料を用いることができる。黄色顔料として、例えば、不溶性アゾ系（ナフトール系及びアニライド系）、溶性アゾ系、キナクリドン系等の有機系顔料や、例えば、クロムエロー、カドミウムイエロー、ニッケルチタンイエロー、黄丹、ストロンチウムクロメート等の無機系顔料を用いることができる。緑色顔料として、例えば有機フタロシアニン系顔料を用いることができる。青色顔料として、例えば、有機フタロシアニン系顔料、ジオキサジン系顔料、紺青、群青、コバルト青、エメラルドグリーン等の無機系顔料を用いることができる。橙色として、例えば、ベンズイミダゾロン系、ピラゾロン系等の有機系顔料を用いることができる。 As the red pigment, for example, organic pigments such as insoluble azo (naphthol and anilide) or soluble azo, and inorganic pigments such as bengara, cadmium red, and red lead can be used. Examples of yellow pigments include organic pigments such as insoluble azo (naphthol and anilide), soluble azo, and quinacridone, and inorganic pigments such as chrome yellow, cadmium yellow, nickel titanium yellow, tan and strontium chromate Pigments can be used. As the green pigment, for example, an organic phthalocyanine pigment can be used. Examples of blue pigments that can be used include inorganic pigments such as organic phthalocyanine pigments, dioxazine pigments, bitumen, ultramarine blue, cobalt blue, and emerald green. For example, an organic pigment such as benzimidazolone or pyrazolone can be used as the orange color.
２－３．絶縁皮膜の表面粗さ
　本発明において、絶縁皮膜の好ましい厚さは１０～５０μｍである。一方、本発明の絶縁皮膜積層金属板を用いて有機電子デバイスを作製する際に、絶縁皮膜の上に形成される導電性薄膜層の好ましい厚さは、後述の通り、０．０１～１μｍである。このように両者の厚さが大幅に異なるため、厚さの小さな導電性薄膜層は厚さが大幅に大きい絶縁皮膜の影響を受けて品質不良が発生し易い。例えば、絶縁皮膜の表面にピンホール等の欠陥が存在すると、水が浸入し易くなり、ダークスポットが出現し易くなる。又、絶縁皮膜に表面凹凸があると、絶縁皮膜の凸部に形成される導電性薄膜層の厚さが絶縁皮膜の凹部に形成される導電性薄膜層の厚さと相違し易くなり、有機電子デバイスの品質や寿命に影響を及ぼし易くなる。このような問題を回避する観点から、絶縁皮膜の３ｍｍ四方の領域における表面粗さは１０ｎｍ以下であることが好ましく、５ｎｍ以下であることがより好ましく、３ｎｍ以下であることがさらに好ましい。これにより、絶縁皮膜が有するうねりも抑制することができる。 2-3. Surface Roughness of Insulating Film In the present invention, the preferable thickness of the insulating film is 10 to 50 μm. On the other hand, when an organic electronic device is produced using the insulating coating laminated metal plate of the present invention, the preferred thickness of the conductive thin film layer formed on the insulating coating is 0.01 to 1 μm as described later. is there. As described above, since the thicknesses of the two are significantly different, the conductive thin film layer having a small thickness is easily affected by an insulating film having a large thickness, so that a quality defect is likely to occur. For example, if there is a defect such as a pinhole on the surface of the insulating film, water easily enters and dark spots are likely to appear. Also, if the insulating film has surface irregularities, the thickness of the conductive thin film layer formed on the convex part of the insulating film tends to be different from the thickness of the conductive thin film layer formed on the concave part of the insulating film. It tends to affect the quality and lifetime of the device. From the viewpoint of avoiding such a problem, the surface roughness in a 3 mm square region of the insulating film is preferably 10 nm or less, more preferably 5 nm or less, and further preferably 3 nm or less. Thereby, the wave | undulation which an insulating film has can also be suppressed.
　３ｍｍ四方の領域における表面粗さは、後述の測定方法により測定することができる。 The surface roughness in a 3 mm square area can be measured by the measurement method described later.
　絶縁皮膜の３ｍｍ四方の領域における表面粗さを１０ｎｍ以下にする方法として、絶縁皮膜の表面に対して化学機械研磨（Ｃｈｅｍｉｃａｌ　Ｍｅｃｈａｎｉｃａｌ　Ｐｏｌｉｓｈｉｎｇ：ＣＭＰ）を行うことを挙げることができる。これにより、絶縁皮膜表面を平滑にすることができる。 As a method for setting the surface roughness in a 3 mm square region of the insulating film to 10 nm or less, chemical mechanical polishing (CMP) may be performed on the surface of the insulating film. Thereby, the insulating film surface can be smoothed.
　化学機械研磨方法は特に限定されておらず、研磨剤自体が有する表面化学作用や研磨液に含まれる化学成分の作用によって研磨される公知の研磨方法を用いればよい。研磨剤も特に限定されておらず、例えば、シリカ、アルミナ、セリア、チタニア、ジルコニア、ゲルマニア等を用いることができる。 The chemical mechanical polishing method is not particularly limited, and a known polishing method in which polishing is performed by the surface chemical action of the polishing agent itself or the action of chemical components contained in the polishing liquid may be used. The abrasive is not particularly limited, and for example, silica, alumina, ceria, titania, zirconia, germania, or the like can be used.
［絶縁皮膜積層金属板の製造方法］
　次に、上記絶縁皮膜積層金属板の製造方法について、説明する。 [Insulating film laminated metal plate manufacturing method]
Next, the manufacturing method of the said insulating-film laminated metal plate is demonstrated.
　絶縁皮膜は、金属板表面又は他の層の上に絶縁皮膜作製用組成物を塗布する塗布法により積層することが好ましい。そのため、絶縁皮膜作製用組成物は液状であって溶媒も含むことが望ましい。絶縁皮膜作製用組成物に用いる溶媒は、絶縁皮膜作製用組成物が含有すべき各成分を溶解又は分散させ得るものであれば、特に制限はない。溶媒として、例えば、メタノール、エタノール、ｎ－プロパノール、イソプロパノール、ｎ－ブタノール、イソブタノール、エチレングリコール等のアルコール類；アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン類；トルエン、ベンゼン、キシレン、ソルベッソ（登録商標）１００（エクソンモービル社製）、ソルベッソ（登録商標）１５０（エクソンモービル社製）等の芳香族炭化水素類；ヘキサン、ヘプタン、オクタン等の脂肪族炭化水素類；酢酸エチル、酢酸ブチル等のエステル類；等を挙げることができる。絶縁皮膜作製用組成物は、例えば上記溶媒を用いて、固形分を調整することができる。 The insulating film is preferably laminated by a coating method in which the composition for forming an insulating film is applied on the surface of the metal plate or on another layer. Therefore, it is desirable that the composition for forming an insulating film is liquid and includes a solvent. If the solvent used for the composition for insulating film preparations can melt | dissolve or disperse | distribute each component which the composition for insulating film preparations should contain, there will be no restriction | limiting in particular. Examples of the solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and ethylene glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; toluene, benzene, xylene, and solvesso Aromatic hydrocarbons such as (registered trademark) 100 (manufactured by ExxonMobil), Solvesso (registered trademark) 150 (manufactured by ExxonMobil); aliphatic hydrocarbons such as hexane, heptane, and octane; ethyl acetate, butyl acetate And the like; and the like. The composition for insulating film preparation can adjust solid content, for example using the said solvent.
　絶縁皮膜作製用組成物の塗布方法は、特に制限されず、既知の方法を適宜採用することができる。塗布方法として、例えば、バーコーター法、ロールコーター法、カーテンフローコーター法、スプレー法、スプレーリンガー法等によるプレコート法を挙げることができる。これらの中でも、コスト等の観点からバーコーター法、ロールコーター法、スプレー法、スプレーリンガー法が好ましい。焼付け温度は、例えば、プレコート法に用いる場合には１９０℃以上２５０℃以下が好ましく、２００℃以上２４０℃以下がより好ましい。乾燥温度は、絶縁皮膜が熱により劣化しない程度であればよく、例えば、１９０～２５０℃程度が好ましく、２００～２４０℃程度がより好ましい。焼付け温度及び乾燥温度として、到達板温（Ｐｅａｋ　Ｍｅｔａｌ　Ｔｅｍｐｅｒａｔｕｒｅ：ＰＭＴ）を用いればよい。 The coating method of the composition for forming an insulating film is not particularly limited, and a known method can be appropriately employed. Examples of the coating method include a precoat method such as a bar coater method, a roll coater method, a curtain flow coater method, a spray method, and a spray ringer method. Among these, the bar coater method, the roll coater method, the spray method, and the spray ringer method are preferable from the viewpoint of cost and the like. For example, the baking temperature is preferably 190 ° C. or higher and 250 ° C. or lower, and more preferably 200 ° C. or higher and 240 ° C. or lower when used in the precoat method. The drying temperature is not limited as long as the insulating film is not deteriorated by heat. For example, the drying temperature is preferably about 190 to 250 ° C., more preferably about 200 to 240 ° C. As the baking temperature and the drying temperature, a reaching plate temperature (PMT) may be used.
　ポリエステル樹脂及び絶縁皮膜積層金属板の製造方法は、例えば、次の通りである。 The manufacturing method of the polyester resin and the insulating coating laminated metal plate is, for example, as follows.
　テレフタル酸及びイソフタルを合計で９０モル％以上含有するジカルボン酸と、炭素数２～５のポリオールを９０モル％以上含有するポリオールとをモル比１：１．５～２で含有するポリエステル樹脂形成用組成物に触媒としての三酸化アンチモンを加え、大気圧下１８０～２１０℃で１８０分間加熱して縮合反応を進行させる。続いて、温度を２５０℃まで昇温させるとともに、圧力を１～５ｍｍＨｇに減圧した後、１８０分間縮合反応をさらに進行させるとともに縮合反応で生じた水を除去する。これにより、ポリエステル樹脂が得られる。後半の水の除去を伴う縮合反応ではポリオールが揮発するため、得られたポリエステル樹脂におけるジカルボン酸由来単位とポリオール由来単位はモル比で略１：１となる。ジカルボン酸及びポリオールの精確な仕込み量は、ジカルボン酸とポリオールの含有比率を変えたポリエステル樹脂形成用組成物から得たポリエステル樹脂におけるジカルボン酸由来単位とポリオール由来単位のモル比に基づいて、決定する。 For forming a polyester resin containing a dicarboxylic acid containing 90 mol% or more of terephthalic acid and isophthal in total and a polyol containing 90 mol% or more of a polyol having 2 to 5 carbon atoms in a molar ratio of 1: 1.5 to 2 Antimony trioxide as a catalyst is added to the composition and heated at 180 to 210 ° C. under atmospheric pressure for 180 minutes to allow the condensation reaction to proceed. Subsequently, the temperature is raised to 250 ° C., the pressure is reduced to 1 to 5 mmHg, and then the condensation reaction is further advanced for 180 minutes and water generated by the condensation reaction is removed. Thereby, a polyester resin is obtained. In the condensation reaction involving the removal of water in the latter half, the polyol volatilizes, so the dicarboxylic acid-derived unit and the polyol-derived unit in the obtained polyester resin are approximately 1: 1 in molar ratio. The exact charge amount of dicarboxylic acid and polyol is determined based on the molar ratio of the dicarboxylic acid-derived unit and the polyol-derived unit in the polyester resin obtained from the polyester resin-forming composition in which the content ratio of the dicarboxylic acid and the polyol is changed. .
　得られたポリエステル樹脂と、架橋剤と、必要に応じて添加される顔料等とを溶剤に溶解させ、分散させて得た溶液（絶縁皮膜作製用組成物）を金属板に塗布し、加熱する。これにより、金属板上に絶縁皮膜が形成されて、絶縁皮膜積層金属板が得られる。上記溶液の作製に際して、固形分（ポリエステル樹脂、架橋剤、顔料等）の含有量は２０～７０質量％であることが好ましい。固形分の含有量が２０質量％未満では、溶液の粘度が低くなり過ぎて、絶縁皮膜の目標厚さに達するまで複数回の塗布を繰り返す必要が生じる。一方、固形分の含有量が７０質量％を超えると、溶液の粘度が高くなり過ぎて塗布自体が困難となる。又、固形分の中の顔料比率は６０質量％以下であることが好ましい。固形分の中の顔料比率が６０質量％を超えると、溶液の粘度が高くなり過ぎて塗布自体が困難となる。 A solution obtained by dissolving and dispersing the obtained polyester resin, a crosslinking agent, and a pigment added if necessary in a solvent (a composition for preparing an insulating film) is applied to a metal plate and heated. . Thereby, an insulating film is formed on the metal plate, and an insulating film laminated metal plate is obtained. In preparing the solution, the solid content (polyester resin, crosslinking agent, pigment, etc.) is preferably 20 to 70% by mass. If the solid content is less than 20% by mass, the viscosity of the solution becomes too low, and it is necessary to repeat the coating several times until the target thickness of the insulating film is reached. On the other hand, if the solid content exceeds 70% by mass, the viscosity of the solution becomes too high and the coating itself becomes difficult. Moreover, it is preferable that the pigment ratio in solid content is 60 mass% or less. When the pigment ratio in the solid content exceeds 60% by mass, the viscosity of the solution becomes too high and coating itself becomes difficult.
［金属基板］
　次に、本発明の他の一局面である金属基板について、説明する。 [Metal substrate]
Next, a metal substrate which is another aspect of the present invention will be described.
　本発明の金属基板は、上記絶縁皮膜積層金属板が有する上記絶縁皮膜の上に導電性薄膜層が積層されたものである。 The metal substrate of the present invention is obtained by laminating a conductive thin film layer on the insulating film of the insulating film laminated metal plate.
　本発明では、導電性薄膜層は例えば、Ａｌ、Ｂ、Ｇａ、Ｓｂ等が添加されたＺｎＯ、ＩＴＯ又はＳｎＯ２によって構成される。通常、ＩＴＯによって構成される。 In the present invention, the conductive thin film layer is made of, for example, ZnO, ITO, or SnO 2 to which Al, B, Ga, Sb, or the like is added. Usually, it is made of ITO.
　導電性薄膜層の層構造は単層構造でもよいし、２層以上の積層構造でもよい。各層を構成する物質（即ち上記ＺｎＯ、ＩＴＯ又はＳｎＯ２）は同一であってもよいし、異なっていてもよい。 The layer structure of the conductive thin film layer may be a single layer structure or a laminated structure of two or more layers. The material constituting each layer (that is, the above ZnO, ITO, or SnO 2 ) may be the same or different.
　導電性薄膜層の厚さは、特に制限されないが、０．０１～１μｍが好ましい。 The thickness of the conductive thin film layer is not particularly limited, but is preferably 0.01 to 1 μm.
　導電性薄膜層の３ｍｍ四方の領域における表面粗さは１００ｎｍ以下であることが好ましく、２０ｎｍ以下であることがより好ましく、１０ｎｍ以下であることがさらに好ましく、５ｎｍ以下であることがより一層好ましい。これにより、発電効率が高い太陽電池や発光照度が高い有機ＥＬ素子を作製することができる。３ｍｍ四方の領域における表面粗さは、後述の測定方法により測定することができる。 The surface roughness in a 3 mm square region of the conductive thin film layer is preferably 100 nm or less, more preferably 20 nm or less, still more preferably 10 nm or less, and even more preferably 5 nm or less. Thereby, a solar cell with high power generation efficiency and an organic EL element with high light emission illuminance can be produced. The surface roughness in a 3 mm square region can be measured by the measurement method described later.
　導電性薄膜層は約２００℃以上の耐熱性を有するので、本発明の金属基板を用いて有機電子デバイスを作製することができる。 Since the conductive thin film layer has a heat resistance of about 200 ° C. or higher, an organic electronic device can be produced using the metal substrate of the present invention.
　本発明の金属基板を用いて作製された有機ＥＬ素子では、導電性薄膜層は陽極として機能する。そして、導電性薄膜層が透明性を有するので、発光層が金属板側に発した光は導電性薄膜層の下に位置する顔料を含有した絶縁皮膜によって反射される。 In the organic EL device manufactured using the metal substrate of the present invention, the conductive thin film layer functions as an anode. And since an electroconductive thin film layer has transparency, the light which the light emitting layer emitted to the metal plate side is reflected by the insulating film containing the pigment located under an electroconductive thin film layer.
［金属基板の製造方法］
　次に、上記金属基板の製造方法について、説明する。 [Metal substrate manufacturing method]
Next, a method for manufacturing the metal substrate will be described.
　上記導電性薄膜層はスパッタリングにより形成される。より具体的には、真空容器内に本発明の絶縁皮膜積層金属板を載置するとともに、薄膜として付与したい金属又は金属酸化物をターゲットとして設置する。例えば、導電性薄膜層としてＩＴＯ層を形成する場合には、ＩＴＯからなるターゲットを用いる。そして、例えばアルゴンのような希ガス元素又は窒素に対して高電圧をかけてイオン化させ、ターゲットに衝突させる。これにより、ターゲット表面の原子等がはじき飛ばされ、絶縁皮膜積層金属板に到達して絶縁皮膜上に導電性薄膜層が形成される。 The conductive thin film layer is formed by sputtering. More specifically, the insulating film laminated metal plate of the present invention is placed in a vacuum vessel, and a metal or metal oxide to be applied as a thin film is set as a target. For example, when an ITO layer is formed as the conductive thin film layer, a target made of ITO is used. Then, for example, a high voltage is applied to a rare gas element such as argon or nitrogen to make it collide with the target. Thereby, atoms and the like on the target surface are repelled, reach the insulating film laminated metal plate, and form a conductive thin film layer on the insulating film.
［サブストレート型薄膜太陽電池］
　次に、本発明の絶縁皮膜積層金属板を備えたサブストレート型薄膜太陽電池について、説明する。 [Substrate type thin film solar cell]
Next, the substrate type thin film solar cell provided with the insulating coating laminated metal plate of the present invention will be described.
　サブストレート型太陽電池は、本発明の絶縁皮膜積層金属板を備えたものであれば、公知のいずれの構造でもよく、例えば、基本的には本発明の絶縁皮膜積層金属板が有する絶縁皮膜上に、裏面電極、光電変換層、表面電極がこの順で積層された構造である。光電変換層は、透明性の表面電極を通過して到達した光を吸収して電流を発生させる層であり、裏面電極及び表面電極は、いずれも光電変換層で発生した電流を取り出すためのものであり、いずれも導電性材料からなる。光入射側の表面電極は透光性を有する必要がある。裏面電極、光電変換層、表面電極については、公知のサブストレート型薄膜太陽電池と同様の材料を用いることができる。 The substrate type solar cell may have any known structure as long as it has the insulating film laminated metal plate of the present invention. For example, the substrate type solar cell basically has an insulating film laminated metal plate of the present invention on the insulating film. Further, the back electrode, the photoelectric conversion layer, and the front electrode are stacked in this order. The photoelectric conversion layer is a layer that generates light by absorbing light that has passed through the transparent surface electrode, and both the back electrode and the surface electrode are for taking out the current generated in the photoelectric conversion layer. Both are made of a conductive material. The surface electrode on the light incident side needs to have translucency. About a back surface electrode, a photoelectric converting layer, and a surface electrode, the material similar to a well-known substrate type thin film solar cell can be used.
　サブストレート型太陽電池では、太陽光は透明性の表面電極側から入射するため、絶縁皮膜積層金属板の透明性は求められない。 In the substrate type solar cell, since sunlight is incident from the transparent surface electrode side, the transparency of the insulating coating laminated metal plate is not required.
［トップエミッション型有機ＥＬ素子］
　次に、本発明の絶縁皮膜積層金属板を備えたトップエミッション型有機ＥＬ素子について、説明する。 [Top emission type organic EL element]
Next, the top emission type organic EL device provided with the insulating film laminated metal plate of the present invention will be described.
　トップエミッション型有機ＥＬ素子は、本発明の絶縁皮膜積層金属板を備えたものであれば、公知のいずれの構造でもよく、例えば、基本的には本発明の絶縁皮膜積層金属板が有する絶縁皮膜上に、陽極、発光層、陰極がこの順に積層された構造である。陽極、発光層、陰極については、公知のトップエミッション型薄膜太陽電池と同様の材料を用いることができる。 The top emission type organic EL element may have any known structure as long as it is provided with the insulating coating laminated metal plate of the present invention. For example, the insulating coating laminated metal plate of the present invention basically has an insulating coating. A structure in which an anode, a light emitting layer, and a cathode are laminated in this order on top. For the anode, the light emitting layer, and the cathode, the same materials as known top emission thin film solar cells can be used.
　トップエミッション型有機ＥＬ素子では、光は陰極を透過して（絶縁皮膜積層金属板を透過することなく）取り出されるため、基板として透明でない金属板を用いることができる。 In the top emission type organic EL element, since light is extracted through the cathode (without passing through the insulating film laminated metal plate), a non-transparent metal plate can be used.
　上述したように、本発明の一局面は、金属板と、当該金属板の少なくとも一方の面側に積層される絶縁皮膜とを有し、上記絶縁皮膜は熱硬化性樹脂を含有し、上記熱硬化性樹脂は、テレフタル酸由来単位及びイソフタル酸由来単位を合計で９０モル％以上含有するジカルボン酸由来単位と、炭素数２～５のポリオール由来単位を９０モル％以上含有するポリオール由来単位とから構成されるポリエステル樹脂を含有し、上記ジカルボン酸由来単位に占める上記テレフタル酸由来単位のモル百分率が４０～７０％であり、上記ジカルボン酸由来単位に占める上記イソフタル酸由来単位のモル百分率が３０～６０％であり、上記式（１）で算出されるポリオール由来単位の調整平均炭素数が３．４以下である、上記絶縁皮膜の上に導電性薄膜層を形成するための絶縁皮膜積層金属板である。 As described above, one aspect of the present invention includes a metal plate and an insulating film laminated on at least one surface side of the metal plate, the insulating film containing a thermosetting resin, and the heat The curable resin comprises a dicarboxylic acid-derived unit containing 90 mol% or more of terephthalic acid-derived units and isophthalic acid-derived units in total, and a polyol-derived unit containing 90 mol% or more of a polyol-derived unit having 2 to 5 carbon atoms. Containing a polyester resin, wherein the molar percentage of the terephthalic acid-derived unit in the dicarboxylic acid-derived unit is 40 to 70%, and the molar percentage of the isophthalic acid-derived unit in the dicarboxylic acid-derived unit is 30 to A conductive thin film layer on the insulating film, wherein the adjusted average carbon number of the polyol-derived unit calculated by the above formula (1) is 60% or less. An insulating film laminated metal sheet for forming.
　この構成によれば、絶縁皮膜の上にスパッタリングによって導電性薄膜層を形成する際、絶縁皮膜の温度上昇に起因した軟化が抑制されるので、しわの発生が抑制された導電性薄膜層が形成される。ひいては、本発明の絶縁皮膜積層金属板を用いて作製された有機ＥＬ素子は発光層表面が均一に発光する。 According to this configuration, when the conductive thin film layer is formed on the insulating film by sputtering, softening due to the temperature rise of the insulating film is suppressed, so that the conductive thin film layer in which the generation of wrinkles is suppressed is formed. Is done. As a result, the surface of the light-emitting layer of the organic EL element produced using the insulating film laminated metal plate of the present invention emits light uniformly.
　本発明の絶縁皮膜積層金属板において、上記絶縁皮膜は顔料をさらに含有することができる。この構成により、本発明の絶縁皮膜積層金属板を用いて作製された有機ＥＬ素子は、絶縁皮膜において当該顔料に対応した波長の光を素子表面側に反射するので、この波長の光に係る輝度を向上させることができる。 In the insulating film laminated metal plate of the present invention, the insulating film may further contain a pigment. With this configuration, the organic EL element produced using the insulating coating laminated metal plate of the present invention reflects light having a wavelength corresponding to the pigment in the insulating coating to the element surface side. Can be improved.
　本発明の絶縁皮膜積層金属板は、上記絶縁皮膜の３ｍｍ四方の領域における表面粗さが１０ｎｍ以下であることが好ましい。この構成により、絶縁皮膜の表面が実用的な範囲で平滑となり、ダークスポットの発生を抑制することができる。そして、本発明の絶縁皮膜積層金属板を用いることで、発電効率が高い太陽電池や発光照度が高い有機ＥＬ素子を作製することができる。 In the insulating coating laminated metal plate of the present invention, the surface roughness in a 3 mm square region of the insulating coating is preferably 10 nm or less. With this configuration, the surface of the insulating film becomes smooth within a practical range, and generation of dark spots can be suppressed. And by using the insulating coating laminated metal plate of this invention, a solar cell with high electric power generation efficiency and an organic EL element with high light emission illumination intensity can be produced.
　本発明の他の一局面は、上記絶縁皮膜積層金属板が有する絶縁皮膜の上に導電性薄膜層が積層された、金属基板である。 Another aspect of the present invention is a metal substrate in which a conductive thin film layer is laminated on an insulating film of the insulating film laminated metal plate.
　この構成によれば、本発明の金属基板を用いて作製された有機ＥＬ素子は、色むらや発光照度不足が生じ難くなり、他方、本発明の金属基板を用いて作製された太陽電池は、発電量が低下し難くなる。 According to this configuration, the organic EL element manufactured using the metal substrate of the present invention is less likely to cause uneven color and insufficient light emission illuminance, while the solar cell manufactured using the metal substrate of the present invention is The amount of power generation is difficult to decrease.
　本発明の金属基板において、上記導電性薄膜層の３ｍｍ四方の領域における表面粗さが１００ｎｍ以下であることが好ましい。この構成により、導電性薄膜層の表面が実用的な範囲で平滑となり、品質や寿命の安定した有機ＥＬ素子や太陽電池を作製することができる。 In the metal substrate of the present invention, it is preferable that the surface roughness in a 3 mm square region of the conductive thin film layer is 100 nm or less. With this configuration, the surface of the conductive thin film layer becomes smooth within a practical range, and an organic EL element or a solar cell with stable quality and lifetime can be manufactured.
　本発明の金属基板は、トップエミッション型有機ＥＬ素子又はサブストレート型薄膜太陽電池に用いることができる。この構成により、発光照度の安定したトップエミッション型有機ＥＬ素子や発電量の安定したサブストレート型薄膜太陽電池を作製することができる。 The metal substrate of the present invention can be used for a top emission type organic EL element or a substrate type thin film solar cell. With this configuration, a top emission type organic EL element with stable emission illuminance and a substrate type thin film solar cell with stable power generation can be manufactured.
　本発明によれば、スパッタリングによる導電性薄膜層形成時にしわの発生を抑制することができる絶縁皮膜積層金属板、及び導電性薄膜層表面でのしわの発生が抑制された金属基板を提供することができる。 According to the present invention, an insulating film laminated metal plate capable of suppressing the generation of wrinkles when forming a conductive thin film layer by sputtering, and a metal substrate in which the generation of wrinkles on the surface of the conductive thin film layer is suppressed are provided. Can do.
　以下、実施例を挙げて本発明をより具体的に説明する。尚、本発明は下記実施例によって制限されず、前・後記の趣旨に適合し得る範囲で変更を加えて実施することは可能であり、それらはいずれも本発明の技術的範囲に包含される。 Hereinafter, the present invention will be described more specifically with reference to examples. It should be noted that the present invention is not limited by the following examples, and can be implemented with modifications within a range that can meet the gist of the preceding and following descriptions, all of which are included in the technical scope of the present invention. .
［ポリエステル樹脂の作製］
　撹拌装置及び温度計を有するオートクレーブにて、表１のＮｏ．１に示すポリエステル樹脂の原料モノマー（仕込み量：テレフタル酸８３．０質量部、イソフタル酸８３．０質量部、エチレングリコール１０７．２質量部、ネオペンチルグリコール４４．８質量部）及び三酸化アンチモン０．１質量部を大気圧下１８０～２１０℃で１８０分間加熱して縮合反応を進行させた。続いて、温度を２５０℃まで昇温させるとともに、圧力を１～５ｍｍＨｇに減圧した後、１８０分間縮合反応をさらに進行させた。これにより、Ｎｏ．１のポリエステル樹脂を得た。 [Production of polyester resin]
In an autoclave having a stirrer and a thermometer, No. 1 in Table 1 was obtained. Raw material monomers (charge amount: terephthalic acid 83.0 parts by mass, isophthalic acid 83.0 parts by mass, ethylene glycol 107.2 parts by mass, neopentyl glycol 44.8 parts by mass) and antimony trioxide 0 .1 part by mass was heated at 180-210 ° C. under atmospheric pressure for 180 minutes to allow the condensation reaction to proceed. Subsequently, the temperature was raised to 250 ° C., the pressure was reduced to 1 to 5 mmHg, and the condensation reaction was further advanced for 180 minutes. As a result, no. 1 polyester resin was obtained.
　ＮＭＲ法によるＮｏ．１のポリエステル樹脂の各構成単位の組成比は、ジカルボン酸由来単位に占めるテレフタル酸由来単位のモル百分率が５０％、ジカルボン酸由来単位に占めるイソフタル酸由来単位のモル百分率が５０％、ポリオール由来単位に占めるエチレングリコール酸由来単位のモル百分率が８０％、ポリオール由来単位に占めるネオペンチルグリコール酸由来単位のモル百分率が２０％であった。 No. by NMR method The composition ratio of each structural unit of the polyester resin 1 is such that the molar percentage of the terephthalic acid-derived unit in the dicarboxylic acid-derived unit is 50%, the molar percentage of the isophthalic acid-derived unit in the dicarboxylic acid-derived unit is 50%, and the polyol-derived unit. The mole percentage of units derived from ethylene glycolic acid in 80% was 80%, and the mole percentage of units derived from neopentyl glycolic acid in units derived from polyol was 20%.
　次に、Ｎｏ．１のポリエステル樹脂の作製条件のうち、原料モノマーの仕込み量のみをＮｏ．１のポリエステル樹脂の原料モノマーから表１のＮｏ．２～９に示すポリエステル樹脂の原料モノマーそれぞれに変更することで、Ｎｏ．２～９のポリエステル樹脂をそれぞれ得た。そして、ＮＭＲ法により、Ｎｏ．２～９のポリエステル樹脂の各構成単位の組成比を得た。その結果を表１に示す。 Next, No. Of the production conditions for the polyester resin of No. 1, only the amount of raw material monomer charged was No. 1. No. 1 in Table 1 from the raw material monomer of the polyester resin of No. 1. By changing to the raw material monomers of the polyester resin shown in 2 to 9, No. 2 to 9 polyester resins were obtained. And by NMR method, it is No. The composition ratio of each structural unit of 2 to 9 polyester resins was obtained. The results are shown in Table 1.
　Ｎｏ．１～９のポリエステル樹脂について、ＮＭＲ法によって得られたポリオール由来単位に占める各由来単位のモル百分率と各由来単位の炭素数とから、ポリオール由来単位の平均炭素数を算出した。そして、ポリオール由来単位の平均炭素数とジカルボン酸由来単位に占めるテレフタル酸由来単位のモル百分率とから、ポリオール由来単位の調整平均炭素数を算出した。これらの算出結果も表１に示す。 No. For the polyester resins 1 to 9, the average carbon number of the polyol-derived unit was calculated from the mole percentage of each derived unit in the polyol-derived unit obtained by NMR method and the carbon number of each derived unit. Then, the adjusted average carbon number of the polyol-derived unit was calculated from the average carbon number of the polyol-derived unit and the molar percentage of the terephthalic acid-derived unit in the dicarboxylic acid-derived unit. These calculation results are also shown in Table 1.
［絶縁皮膜作製用組成物の作製］
　キシレン（沸点：１４０℃）とシクロヘキサノン（沸点：１５６℃）とを等量ずつ混合した溶媒に、Ｎｏ．１のポリエステル樹脂を固形分換算で４３．４質量部、メラミン樹脂（ＤＩＣ株式会社製スーパーベッカミン（登録商標）Ｊ－８２０－６０）を固形分換算で１４．５質量部、酸化チタン粒子（石原産業株式会社製タイペーク（登録商標）ＣＲ－５０（平均粒子径０．２５μｍ））を固形分換算で１６．０質量部加えて、最後に東京化成工業株式会社製のトリエチレンジアミンを０．３質量部加えて、Ｎｏ．１の絶縁皮膜作製用組成物を得た。尚、ポリエステル樹脂とメラミン樹脂との合計の固形分が５８質量％となるようにキシレンとシクロヘキサノンとの混合溶媒の量を調整した。 [Preparation of composition for insulating film preparation]
In a solvent in which xylene (boiling point: 140 ° C.) and cyclohexanone (boiling point: 156 ° C.) are mixed in equal amounts, 13.4 parts by weight of a polyester resin in terms of solids, 14.5 parts by weight of melamine resin (Super Becamine (registered trademark) J-820-60, manufactured by DIC Corporation) in terms of solids, titanium oxide particles ( 16.0 parts by mass in terms of solid content was added to Taipek (registered trademark) CR-50 (average particle size: 0.25 μm) manufactured by Ishihara Sangyo Co., Ltd., and finally, triethylenediamine manufactured by Tokyo Chemical Industry Co., Ltd. was added to 0.3 In addition to parts by mass, no. 1 was obtained. The amount of the mixed solvent of xylene and cyclohexanone was adjusted so that the total solid content of the polyester resin and melamine resin was 58% by mass.
　次に、Ｎｏ．１の絶縁皮膜作製用組成物の作製条件のうち、配合するポリエステル樹脂のみをＮｏ．１のポリエステル樹脂からＮｏ．２～９のポリエステル樹脂それぞれに変更することで、Ｎｏ．２～９の絶縁皮膜作製用組成物をそれぞれ得た。 Next, No. Among the preparation conditions of the composition for producing an insulating film of No. 1, only the polyester resin to be blended is No. 1 polyester resin No. 1 By changing to each of 2 to 9 polyester resins, no. 2 to 9 insulating film preparation compositions were obtained.
［絶縁皮膜積層金属板の作製］
　金属板として、板厚０．８ｍｍ、金属板両面における各面当たりの亜鉛めっき付着量２０ｇ／ｍ２の電気純亜鉛めっき鋼板を用いて、当該金属板の表面にＮｏ．１の絶縁皮膜作製用組成物を膜厚が１５μｍとなるようにバーコーターで塗布した。そして、到達板温が２２０℃となるように２分間焼付けて乾燥させることにより、Ｎｏ．１の絶縁皮膜積層金属板を得た。 [Preparation of laminated metal sheet with insulating film]
As the metal plate, an electropure galvanized steel plate having a plate thickness of 0.8 mm and a galvanized coating amount of 20 g / m 2 on each side of both sides of the metal plate was used. 1 composition for insulating film preparation was applied with a bar coater so that the film thickness was 15 μm. And it is baked for 2 minutes so that the ultimate plate temperature becomes 220 ° C., and then dried. Insulating film laminated metal plate 1 was obtained.
　次に、Ｎｏ．１の絶縁皮膜積層金属板の作製条件のうち、塗布する絶縁皮膜作製用組成物のみをＮｏ．１の絶縁皮膜作製用組成物からＮｏ．２～９の絶縁皮膜作製用組成物それぞれに変更することで、Ｎｏ．２～９の絶縁皮膜積層金属板をそれぞれ得た。 Next, No. Among the conditions for producing the insulating film laminated metal plate of No. 1, only the composition for producing the insulating film to be applied is No. 1. No. 1 from the composition for preparing an insulating film No. 1 By changing to each of the compositions for preparing an insulating film of 2 to 9, No. Two to nine insulating film laminated metal plates were obtained.
［絶縁皮膜積層金属板の表面研磨］
　研磨装置の基板取り付け用の吸着パッドを貼り付けたホルダーにＮｏ．１の絶縁皮膜積層金属板をセットし、絶縁皮膜を下にして研磨装置の定盤に取り付けた研磨パッド上にセットした。研磨剤として、粒径が約１００ｎｍのアルミナ粒子を用い、圧力６５ｇｆ／ｃｍ２、１周当たりの回転距離を１ｍ、Ｎｏ．１の絶縁皮膜積層金属板と定盤との各回転速度５０ｒｐｍで１分間化学機械研磨を行った。 [Surface polishing of insulating metal film]
No. is attached to the holder to which the suction pad for mounting the substrate of the polishing apparatus is attached. 1 was set on a polishing pad attached to a surface plate of a polishing apparatus with the insulating film facing down. As the abrasive, alumina particles having a particle size of about 100 nm were used, the pressure was 65 gf / cm 2 , the rotational distance per revolution was 1 m, Chemical mechanical polishing was performed for 1 minute at each rotation speed of 50 rpm between the insulating film laminated metal plate 1 and the surface plate.
　次に、Ｎｏ．１の絶縁皮膜積層金属板の表面研磨条件と同一の条件で、Ｎｏ．２～９の絶縁皮膜積層金属板の表面研磨を行った。 Next, No. No. 1 under the same conditions as the surface polishing conditions of the insulating coating laminated metal plate, Surface polishing was performed on 2 to 9 insulating film laminated metal plates.
［金属基板の作製］
　絶縁皮膜の表面が化学機械研磨されたＮｏ．１の絶縁皮膜積層金属板を次の手順で洗浄した。即ち、Ｎｏ．１の絶縁皮膜積層金属板を、まず超純水による洗浄を行い、次に超純水による超音波洗浄を２３ｋＨｚで３分間行い、次に有機物系不純物除去用洗剤による超音波洗浄を２３ｋＨｚで３分間行い、次に超純水による洗浄を行い、次にイオン系不純物除去用洗剤による超音波洗浄を４３ｋＨｚで３分間行い、次に超純水による洗浄を行い、次に超純水による超音波洗浄を１ＭＨｚで３分間行い、次にイソプロピルアルコール蒸気洗浄を行い、ＩＴＯ層の形成直前にＵＶオゾン洗浄を行った。続いて、スパッタリング条件３００Ｗで絶縁皮膜の上に厚さ１００ｎｍのＩＴＯ層を形成することにより、Ｎｏ．１の金属基板を得た。 [Production of metal substrate]
The surface of the insulating film was chemically mechanically polished. The insulating film laminated metal plate 1 was washed by the following procedure. That is, no. 1 is first cleaned with ultrapure water, then ultrasonically cleaned with ultrapure water for 3 minutes at 23 kHz, and then ultrasonically cleaned with a detergent for removing organic substances at 23 kHz for 3 minutes. And then cleaning with ultrapure water, followed by ultrasonic cleaning with a detergent for removing ionic impurities at 43 kHz for 3 minutes, then cleaning with ultrapure water, and then ultrasonication with ultrapure water. Cleaning was performed at 1 MHz for 3 minutes, followed by isopropyl alcohol vapor cleaning, and UV ozone cleaning immediately before the formation of the ITO layer. Subsequently, by forming an ITO layer having a thickness of 100 nm on the insulating film under sputtering conditions of 300 W, No. 1 was obtained. 1 metal substrate was obtained.
　次に、Ｎｏ．１の金属基板の作製条件のうち、金属基板のみをＮｏ．１の金属基板からＮｏ．２～９の金属基板それぞれに変更することで、Ｎｏ．２～９の金属基板をそれぞれ得た。 Next, No. No. 1 of the metal substrate production conditions, only the metal substrate is No. 1. No. 1 from No. 1 metal substrate. By changing to each of 2 to 9 metal substrates, No. 2 to 9 metal substrates were obtained.
［しわ有無の判定］
　Ｎｏ．１～９の金属基板それぞれに対して、原子間力顕微鏡（Ａｔｏｍｉｃ Ｆｏｒｃｅ Ｍｉｃｒｏｓｃｏｐｅ：ＡＦＭ）（セイコー電子工業製ＳＰＩ３８００Ｎ）を用いて、次の判定条件に従ってしわの有無を判定した。 [Determination of wrinkle presence]
No. For each of the metal substrates 1 to 9, an atomic force microscope (AFM) (SPI3800N manufactured by Seiko Denshi Kogyo Co., Ltd.) was used to determine the presence or absence of wrinkles according to the following determination conditions.
（しわ有無の判定条件）
　原子間力顕微鏡を用いて金属基板のＩＴＯ層表面を観察し、ＩＴＯ層表面１００μｍ四方の領域において、長さ２０～５０μｍで幅５～１０μｍで高さ１００ｎｍ以上の凸群が観察された場合をしわ有と判定し、観察されなかった場合をしわ無と判定する。 (Writing condition for wrinkles)
When the surface of the ITO layer of the metal substrate is observed using an atomic force microscope, and a convex group having a length of 20 to 50 μm, a width of 5 to 10 μm, and a height of 100 nm or more is observed in a 100 μm square region of the ITO layer surface. It is determined that wrinkles are present, and a case where no wrinkles are observed is determined as wrinkles free.
　判定結果を表１に示す。 Table 1 shows the judgment results.
　図２は、Ｎｏ．１の金属基板におけるＩＴＯ層表面の原子間力顕微鏡像であり、ＩＴＯ層表面にしわが無いことを示す。図３は、Ｎｏ．２の金属基板におけるＩＴＯ層表面の原子間力顕微鏡像であり、ＩＴＯ層表面にしわが有ることを示す。 Figure 2 shows No. It is an atomic force microscope image of the ITO layer surface in 1 metal substrate, and shows that there is no wrinkle on the ITO layer surface. FIG. It is an atomic force microscope image of the ITO layer surface in 2 metal substrates, and shows that the ITO layer surface has wrinkles.
［３ｍｍ四方の領域における表面粗さの測定］
　表面研磨が行われたＮｏ．１～９の絶縁皮膜積層金属板それぞれの絶縁皮膜に対して、上記原子間力顕微鏡を用いて、次の測定方法に従って３ｍｍ四方の領域における表面粗さＲａ’を測定した。又、Ｎｏ．１～９の金属基板それぞれのＩＴＯ層に対しても、上記原子間力顕微鏡を用いて３ｍｍ四方の領域における表面粗さＲａ’を測定した。 [Measurement of surface roughness in a 3 mm square area]
No. for which surface polishing was performed. The surface roughness Ra ′ in a 3 mm square region was measured for each of the insulating coatings 1 to 9 using the atomic force microscope according to the following measurement method. No. The surface roughness Ra ′ in a 3 mm square region was also measured for the ITO layers of the metal substrates 1 to 9 using the atomic force microscope.
（３ｍｍ四方の領域における表面粗さの測定方法）
　原子間力顕微鏡を用いて、３ｍｍ四方の領域の四隅及び中央部の５箇所において、ＪＩＳ　Ｂ　０６０１に規定された算術平均粗さの定義に基づいて、１０μｍ四方の領域の一方向の算術平均粗さＲａ１及びそれに垂直な方向の算術平均粗さＲａ２を測定する。そして、Ｒａ１とＲａ２の平均値を１０μｍ四方の領域の表面粗さＲａ３とする。そして、上記５箇所の１０μｍ四方の領域の表面粗さＲａ３の平均値を３ｍｍ四方の領域における表面粗さＲａ’とする。 (Measurement method of surface roughness in 3mm square area)
Based on the definition of arithmetic mean roughness defined in JIS B 0601, the unidirectional arithmetic mean roughness of a 10 μm square area is measured at five locations at the four corners and the center of the 3 mm square area using an atomic force microscope. The thickness Ra1 and the arithmetic average roughness Ra2 in the direction perpendicular thereto are measured. And let the average value of Ra1 and Ra2 be surface roughness Ra3 of a 10 micrometer square area | region. The average value of the surface roughness Ra3 of the five 10 μm square regions is defined as the surface roughness Ra ′ in the 3 mm square region.
　測定結果を表１に示す。 Table 1 shows the measurement results.
［Ｎｏ．１～９の絶縁皮膜積層金属板及び金属基板に対する評価］
　Ｎｏ．１、５～７の絶縁皮膜積層金属板及び金属基板は、本発明で規定する各条件を満足する例である。これらは、ＩＴＯ層表面にしわが無く、３ｍｍ四方の領域における表面粗さＲａ’が１００ｎｍ以下であることを示した。 [No. Evaluation of 1 to 9 insulation coating laminated metal plates and metal substrates]
No. The insulating film laminated metal plates 1 and 5 to 7 and the metal substrate are examples satisfying the conditions defined in the present invention. These showed that there was no wrinkle on the surface of the ITO layer and the surface roughness Ra ′ in a 3 mm square region was 100 nm or less.
　一方、Ｎｏ．２～４、８、９の絶縁皮膜積層金属板及び金属基板は、本発明で規定する条件「ポリオール由来単位の調整平均炭素数が３．４以下であること」を満たさない例である。これらは、ＩＴＯ層表面にしわが有り、３ｍｍ四方の領域における表面粗さＲａ’が１００ｎｍを超えていることを示した。 On the other hand, No. The insulating film laminated metal plates and metal substrates of 2 to 4, 8, and 9 are examples that do not satisfy the condition “the adjusted average carbon number of the polyol-derived unit is 3.4 or less” defined in the present invention. These showed that the ITO layer surface had wrinkles and the surface roughness Ra 'in a 3 mm square region exceeded 100 nm.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　この出願は、２０１７年３月３０日に出願された日本国特許出願特願２０１７－０６８８１８号を基礎とするものであり、その内容は、本願に含まれるものである。 This application is based on Japanese Patent Application No. 2017-068818 filed on March 30, 2017, the contents of which are included in this application.
　本発明を表現するために、上述において実施形態を通して本発明を適切且つ十分に説明したが、当業者であれば上述の実施形態を変更及び／又は改良することは容易に為し得ることであると認識すべきである。従って、当業者が実施する変更形態又は改良形態が、請求の範囲に記載された請求項の権利範囲を逸脱するレベルのものでない限り、当該変更形態又は当該改良形態は、当該請求項の権利範囲に包括されると解釈される。 In order to express the present invention, the present invention has been described above and properly through the embodiments. However, those skilled in the art can easily change and / or improve the above-described embodiments. Should be recognized. Therefore, unless the modifications or improvements implemented by those skilled in the art are at a level that departs from the scope of the claims recited in the claims, the modifications or improvements are not limited to the scope of the claims. To be construed as inclusive.

Claims (6)

  1. 　金属板と、当該金属板の少なくとも一方の面側に積層される絶縁皮膜とを有し、
    　前記絶縁皮膜は熱硬化性樹脂を含有し、
    　前記熱硬化性樹脂は、テレフタル酸由来単位及びイソフタル酸由来単位を合計で９０モル％以上含有するジカルボン酸由来単位と、炭素数２～５のポリオール由来単位を９０モル％以上含有するポリオール由来単位とから構成されるポリエステル樹脂を含有し、
    　前記ジカルボン酸由来単位に占める前記テレフタル酸由来単位のモル百分率が４０～７０％であり、
    　前記ジカルボン酸由来単位に占める前記イソフタル酸由来単位のモル百分率が３０～６０％であり、
    　下記式（１）で算出されるポリオール由来単位の調整平均炭素数が３．４以下である、前記絶縁皮膜の上に導電性薄膜層を形成するための絶縁皮膜積層金属板。
    Figure JPOXMLDOC01-appb-M000001
         A metal plate and an insulating film laminated on at least one surface side of the metal plate;
    The insulating film contains a thermosetting resin,
    The thermosetting resin comprises a dicarboxylic acid-derived unit containing 90 mol% or more of terephthalic acid-derived units and isophthalic acid-derived units, and a polyol-derived unit containing 90 mol% or more of a polyol-derived unit having 2 to 5 carbon atoms. A polyester resin composed of
    The molar percentage of the terephthalic acid-derived unit in the dicarboxylic acid-derived unit is 40 to 70%,
    The mole percentage of the isophthalic acid-derived unit in the dicarboxylic acid-derived unit is 30 to 60%,
    The insulating film laminated metal plate for forming a conductive thin film layer on the said insulating film whose adjustment average carbon number of the polyol origin unit calculated by following formula (1) is 3.4 or less.
    Figure JPOXMLDOC01-appb-M000001
  2. 　前記絶縁皮膜は顔料をさらに含有する、請求項１に記載の絶縁皮膜積層金属板。 The insulating coating laminated metal plate according to claim 1, wherein the insulating coating further contains a pigment.
  3. 　前記絶縁皮膜の３ｍｍ四方の領域における表面粗さが１０ｎｍ以下である、請求項１又は２に記載の絶縁皮膜積層金属板。 The insulating film laminated metal plate according to claim 1 or 2, wherein a surface roughness in a 3 mm square region of the insulating film is 10 nm or less.
  4. 　請求項１～３のいずれか一項に記載の絶縁皮膜積層金属板が有する絶縁皮膜の上に導電性薄膜層が積層された、金属基板。 A metal substrate in which a conductive thin film layer is laminated on an insulating film of the insulating film laminated metal plate according to any one of claims 1 to 3.
  5. 　前記導電性薄膜層の３ｍｍ四方の領域における表面粗さが１００ｎｍ以下である、請求項４に記載の金属基板。 The metal substrate according to claim 4, wherein a surface roughness in a 3 mm square region of the conductive thin film layer is 100 nm or less.
  6. 　トップエミッション型有機ＥＬ素子又はサブストレート型薄膜太陽電池に用いられる、請求項４又は５に記載の金属基板。 The metal substrate according to claim 4 or 5, which is used for a top emission type organic EL element or a substrate type thin film solar cell.
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