WO2018180410A1 - 絶縁皮膜積層金属板及び金属基板 - Google Patents

絶縁皮膜積層金属板及び金属基板 Download PDF

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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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insulating film
metal plate
derived unit
polyol
acid
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PCT/JP2018/009414
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English (en)
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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Priority to CN201880019455.4A priority Critical patent/CN110494281B/zh
Priority to KR1020197031612A priority patent/KR102338975B1/ko
Priority to MYPI2019005724A priority patent/MY193148A/en
Publication of WO2018180410A1 publication Critical patent/WO2018180410A1/ja

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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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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5945319A (ja) * 1982-09-06 1984-03-14 Nippon Synthetic Chem Ind Co Ltd:The ポリエステル樹脂の製造法
JPS6227470A (ja) * 1985-07-30 1987-02-05 Toagosei Chem Ind Co Ltd 金属用下塗塗料組成物
JPH03121173A (ja) * 1989-10-04 1991-05-23 Nippon Ester Co Ltd 塗装鋼板用塗料組成物
JPH0762295A (ja) * 1993-08-25 1995-03-07 Dainippon Ink & Chem Inc 塗料用樹脂組成物
WO2016158678A1 (ja) * 2015-03-31 2016-10-06 株式会社神戸製鋼所 金属基板
JP2016195162A (ja) * 2015-03-31 2016-11-17 株式会社神戸製鋼所 金属基板

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DE102011101395A1 (de) * 2011-05-13 2012-11-15 Daimler Ag Verfahren zur Optimierung eines Leistungsbedarfs eines Kraftfahrzeugs
WO2014157601A1 (ja) * 2013-03-28 2014-10-02 株式会社神戸製鋼所 金属基板、それを用いたサブストレート型薄膜太陽電池及びトップエミッション型有機ｅｌ素子
JP6227470B2 (ja) * 2014-04-15 2017-11-08 株式会社ニューギン 遊技機
JP2016193580A (ja) 2015-04-01 2016-11-17 新日鐵住金株式会社 半導体基板用塗装金属板

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5945319A (ja) * 1982-09-06 1984-03-14 Nippon Synthetic Chem Ind Co Ltd:The ポリエステル樹脂の製造法
JPS6227470A (ja) * 1985-07-30 1987-02-05 Toagosei Chem Ind Co Ltd 金属用下塗塗料組成物
JPH03121173A (ja) * 1989-10-04 1991-05-23 Nippon Ester Co Ltd 塗装鋼板用塗料組成物
JPH0762295A (ja) * 1993-08-25 1995-03-07 Dainippon Ink & Chem Inc 塗料用樹脂組成物
WO2016158678A1 (ja) * 2015-03-31 2016-10-06 株式会社神戸製鋼所 金属基板
JP2016195162A (ja) * 2015-03-31 2016-11-17 株式会社神戸製鋼所 金属基板

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TW201843210A (zh) 2018-12-16
MY193148A (en) 2022-09-26
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CN110494281B (zh) 2021-11-26
TWI758444B (zh) 2022-03-21

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