WO2006006498A1 - 樹脂被覆金属板 - Google Patents
樹脂被覆金属板 Download PDFInfo
- Publication number
- WO2006006498A1 WO2006006498A1 PCT/JP2005/012587 JP2005012587W WO2006006498A1 WO 2006006498 A1 WO2006006498 A1 WO 2006006498A1 JP 2005012587 W JP2005012587 W JP 2005012587W WO 2006006498 A1 WO2006006498 A1 WO 2006006498A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- resin
- conductive particles
- resin layer
- coated metal
- metal sheet
- Prior art date
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 78
- 239000011347 resin Substances 0.000 title claims abstract description 78
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 45
- 239000002184 metal Substances 0.000 title claims abstract description 45
- 239000002245 particle Substances 0.000 claims abstract description 97
- 238000009826 distribution Methods 0.000 claims abstract description 17
- 230000001186 cumulative effect Effects 0.000 claims abstract description 10
- 239000003822 epoxy resin Substances 0.000 claims description 22
- 229920000647 polyepoxide Polymers 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 238000012360 testing method Methods 0.000 claims description 10
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 8
- 238000005452 bending Methods 0.000 claims description 6
- 229910000805 Pig iron Inorganic materials 0.000 claims description 3
- 238000005336 cracking Methods 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 230000007797 corrosion Effects 0.000 description 14
- 229910000831 Steel Inorganic materials 0.000 description 13
- 239000010959 steel Substances 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 9
- 239000011342 resin composition Substances 0.000 description 8
- 239000003429 antifungal agent Substances 0.000 description 7
- 229940121375 antifungal agent Drugs 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- 229920000877 Melamine resin Polymers 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229920000768 polyamine Polymers 0.000 description 6
- 239000004640 Melamine resin Substances 0.000 description 5
- 239000002390 adhesive tape Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 230000004580 weight loss Effects 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229910001335 Galvanized steel Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 3
- 239000000539 dimer Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000008397 galvanized steel Substances 0.000 description 3
- VAKIVKMUBMZANL-UHFFFAOYSA-N iron phosphide Chemical compound P.[Fe].[Fe].[Fe] VAKIVKMUBMZANL-UHFFFAOYSA-N 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 150000007974 melamines Chemical class 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical class [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002923 oximes Chemical class 0.000 description 2
- 229920000962 poly(amidoamine) Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 1
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- XXKOQQBKBHUATC-UHFFFAOYSA-N cyclohexylmethylcyclohexane Chemical compound C1CCCCC1CC1CCCCC1 XXKOQQBKBHUATC-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- -1 heterocyclic diamine Chemical class 0.000 description 1
- ZHDTXTDHBRADLM-UHFFFAOYSA-N hydron;2,3,4,5-tetrahydropyridin-6-amine;chloride Chemical compound Cl.NC1=NCCCC1 ZHDTXTDHBRADLM-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- GKQPCPXONLDCMU-CCEZHUSRSA-N lacidipine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C1=CC=CC=C1\C=C\C(=O)OC(C)(C)C GKQPCPXONLDCMU-CCEZHUSRSA-N 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- KYCGURZGBKFEQB-UHFFFAOYSA-N n',n'-dibutylpropane-1,3-diamine Chemical compound CCCCN(CCCC)CCCN KYCGURZGBKFEQB-UHFFFAOYSA-N 0.000 description 1
- ITZPOSYADVYECJ-UHFFFAOYSA-N n'-cyclohexylpropane-1,3-diamine Chemical compound NCCCNC1CCCCC1 ITZPOSYADVYECJ-UHFFFAOYSA-N 0.000 description 1
- ZETYUTMSJWMKNQ-UHFFFAOYSA-N n,n',n'-trimethylhexane-1,6-diamine Chemical compound CNCCCCCCN(C)C ZETYUTMSJWMKNQ-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000007591 painting process Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
-
- 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
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/12—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain a coating with specific electrical properties
-
- 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
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
- C09D5/084—Inorganic compounds
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/254—Polymeric or resinous material
Definitions
- the present invention relates to a resin-coated metal sheet, and more particularly to an automotive anti-corrosion coated steel sheet.
- organic coating coated steel sheets containing iron phosphide as conductive particles have been studied (for example, see Patent Documents 1 and 2).
- Organic coating coated steel sheets containing iron phosphide have the advantages that they are cheaper, have better scratch resistance, better corrosion resistance on the machined part, and have higher weld hit points than Zn grain types.
- Patent Document 1 Japanese Patent Laid-Open No. 11 5269
- Patent Document 2 Japanese Patent Laid-Open No. 11-216420
- the present invention has been made in view of such circumstances, and it is an object of the present invention to provide a resin-coated metal sheet excellent in workability, in particular, exfoliation resistance, as well as weldability and corrosion resistance. To do. Means for solving the problem
- the present invention provides a resin-coated metal plate in which a resin layer containing conductive particles is provided on the surface of a metal plate as means for solving the above-described problem, and the resin layer ),
- the volume average particle size of the conductive particles is r (m)
- the cumulative particle size distribution of the conductive particles is 84%
- the particle size is d (m)
- the cumulative rate is 16%.
- the particle diameter of d (m)
- the film thickness t of the resin layer containing conductive particles is set to 2.0 ⁇ m or more and 16 ⁇ m or less.
- the film thickness of the resin layer affects the manufacturing cost, weldability, corrosion resistance, etc. 2. By making it O -zm or more and 16 m or less, it has excellent manufacturing cost, weldability and corrosion resistance. Is obtained.
- the film thickness t and the volume average particle diameter! Satisfy the above formula (2).
- conductive particles having an appropriate volume average particle diameter! According to the film thickness t of the resin layer.
- the particle size distribution and the volume average diameter r of the conductive particles satisfy the above formula (3).
- SD is an index of the particle size distribution. The larger the SD, the wider the particle size distribution, and the smaller the SD, the narrower the particle size distribution. Then, by defining as in the above formula (3), it is possible to disperse the conductive particles having a uniform particle diameter in the resin layer having a constant film thickness t, and to prevent the conductive particles from falling off and to withstand the resistance. Peelability can be improved.
- the resin-coated metal sheet of the present invention has weldability, corrosion resistance, and workability (in particular, resistance to the resin layer). Excellent peelability.
- the resin-coated metal sheet of the present invention is used as an anti-corrosion coated steel sheet for automobiles, it is possible to omit one automobile painting process, increase production efficiency during automobile production, and reduce production costs. Can do.
- FIG. 1 is a schematic diagram showing an outline of a bending test apparatus.
- the resin-coated metal plate of the present invention has a resin layer containing conductive particles provided on the surface of the metal plate, the film thickness of the resin layer being tm), and the volume average of the conductive particles Particle diameter 3 ⁇ 4: ( ⁇ m), cumulative particle diameter distribution of the conductive particles in the cumulative particle size distribution of 84% dm),
- a resin layer containing conductive particles! I will explain in a moment.
- the resin component constituting the resin layer containing conductive particles include epoxy resin, acrylic resin, urethane resin, and polyester resin, and epoxy resin is preferred. More preferably, a flexible epoxy resin is used. If flexible epoxy resin is used, it has the power to improve powdering resistance during processing.
- the flexible epoxy resin refers to one having a bending number of 300 or more until cracking occurs in the MLT bending test.
- the clamp of the test equipment shown in Fig. 1 is bent with one end of a test piece of width: 15mm and length: 130mm. The other end of the test piece is tension: lkgf, rotation angle 135 °, rotation vibration : 175 times This is a test to measure the number of times until power is generated under the condition of Z minutes and cracks occur.
- urethane-modified epoxy resin and dimer acid-modified epoxy resin are preferably used.
- the urethane-modified epoxy resin is obtained by introducing a urethane bond (resin) into the molecular structure of epoxy resin. Flexibility is imparted by the urethane resin structure.
- Examples of the dimer acid-modified epoxy resin include “Epicoat 872” manufactured by Japan Epoxy Resin.
- the epoxy resin may be either liquid or solid. In the case of a solid, for example, it may be diluted with a solvent.
- the resin layer in the present invention is obtained by curing the above-described resin component with a curing agent.
- curing agents include blocked isocyanates, melamine resins, and amine hardeners. Among them, blocked isocyanate and melamine resin react with the hydroxyl group of epoxy resin, and amine curing agent reacts with the epoxy group of epoxy resin to cure the epoxy resin.
- the reactive ratio of the reactive group of the epoxy resin and the equivalent ratio of the reactive group of the curing agent is preferably 0.8 or more and 1.2 or less.
- Examples of the blocked isocyanate include those obtained by blocking an isocyanate group with force prolatatam, oxime, etc., for example, those blocked with force prolatatum are dissociated at around 150 ° C. However, when blocked with oxime, the blocking agent dissociates at 120 to 130 ° C., and the isocyanate group becomes active.
- Examples of the melamine resin include n-butylated melamine resin, isobutylated melamine resin, and methylated melamine resin.
- Examples of the amine curing agent include aliphatic polyamines, alicyclic polyamines, aromatic polyamines, and polyamidoamines.
- Examples of the aliphatic polyamine include diethylenetriamine, dipropylenetriamine, triethylenetetramine, tetraethylenepentamine, dimethylaminopropylamine, jetylaminopropylamine, and dibutylaminopropylamine.
- Examples include xamethylenediamine, N-aminoethylpiperazine, bis-aminopropylpiperazine, and trimethylhexamethylenediamine.
- Examples of the alicyclic polyamine include 3,3'-dimethyl-4,4'-diaminodicyclohexylenomethane, 3-amino-1-cyclohexylaminopropane, 4,4 and diamino.
- Examples thereof include dicyclohexylmethane, isophorone diamine, 1,3-bis (aminomethyl) cyclohexane, N-dimethyl cyclohexylamine, and heterocyclic diamine.
- aromatic polyamine examples include xylylenediamine, 4,4'-diaminodiphenylmethane, 4,4 diaminodiphenyl ether, diaminodiphenylsulfone, and m-phenylenediamine.
- polyamidoamine examples include polyamide coconut resin and polyaminoamide.
- the conductive particles are not particularly limited as long as they are conductive particles, and include nickel, zinc, aluminum, silver, copper, and other metal powders, carbon black, iron phosphide, zinc oxide, titanium oxide, and the like. Can be used.
- the conductive particles may be used alone or in combination of two or more. It is particularly preferable to use phosphorous iron as the conductive particles. This is because the use of linny pig iron can further improve weldability and workability.
- the content of the conductive particles in the resin layer is preferably 40% by mass or more, more preferably 45% by mass or more. If the content of the conductive particles is less than 40% by mass, the workability is good, but the weldability may be lowered.
- the content of the conductive particles in the resin layer is desirably 60% by mass or less, more preferably 55% by mass or less. This is because if the content of the conductive particles exceeds 60% by mass, the power workability with good weldability is lowered.
- the film thickness t m) of the resin layer containing conductive particles satisfies the following formula.
- the film thickness t of the resin layer containing conductive particles is 2.0 m or more, more preferably 4 ⁇ m or more, 16 ⁇ m or less, more preferably 8 ⁇ m.
- the thickness of the resin layer is less than 2.0 m, the corrosion resistance may be reduced.
- the conductive particles may protrude from the resin layer due to the relatively large particle size of the conductive particles, which may further reduce the corrosion resistance of the resin layer.
- the thickness t of the resin layer exceeds 16 m, the weldability may be deteriorated.
- the conductive particles having an appropriate volume average particle diameter r according to the film thickness t of the resin layer. If the volume average particle size r is made extremely small with respect to t (r ⁇ 0.25t), the weldability decreases due to an increase in the welding current point. On the other hand, if the volume average particle diameter r is too large with respect to the film thickness t (r> 2t), the conductive particles fall off.
- the volume average particle diameter r is more preferably 0.3 t or more and 1.8 t or less! /.
- the particle size distribution SD of the conductive particles and the volume average particle size r are set to satisfy the following formula.
- SD (d -d) Z2 is an index of the particle size distribution
- SD is
- the conductive particles whose particle size distribution is controlled are uniformly dispersed in the resin layer having a constant film thickness t. Can be prevented, and the peel resistance can be improved.
- the proportion of large conductive particles that adversely affect the peeling increases, and the conductive particles fall off, resulting in a decrease in the peelability during processing.
- the SD is more preferably 0.6r or less.
- conductive particles satisfying the above formulas (2) and (3) used in the present invention commercially available conductive particles are purchased and pulverized with a ball mill or the like to obtain a sieve or mesh. It can be obtained from cocoon by using and sizing. In other words, a plurality of types of meshes with coarse meshes are used so that the diameter of the grains is almost within a predetermined range.
- the conductive particles are available as, for example, a product of Glenn Spring Holdings.
- the resin layer in the present invention may contain, for example, an antifungal agent or an anti-settling agent in addition to the above-described oil resin component and conductive particles. Corrosion resistance can be further improved by including an antifungal agent.
- the antifungal agent include aluminum tripolyphosphate and calcium. Examples thereof include muon-exchangeable silica and amorphous magnesium silicate compounds.
- the content of the antifungal agent is preferably 5% by mass or more, more preferably 8% by mass or more in the resin layer. This is because the corrosion resistance can be further improved by setting the content to 5% by mass or more. Further, the content of the antifungal agent is preferably 25% by mass or less, more preferably 20% by mass or less in the resin layer. This is because if the addition amount of the antifungal agent exceeds 25% by mass, the workability deteriorates.
- a zinc-plated metal plate is preferably used as the metal plate provided with the resin layer.
- the zinc-plated metal plate is not particularly limited as long as the metal plate is zinc-plated.
- electrogalvanized steel plate (EG), hot-dip zinc-plated steel plate (GI), Examples include galvannealed steel sheets (GA).
- EG electrogalvanized steel plate
- GI hot-dip zinc-plated steel plate
- G galvannealed steel sheets
- the resin-coated metal plate of the present invention is a resin composition that forms a resin layer, such as a solution, an aqueous solution, an emulsion, conductive particles, and if necessary, an antifungal agent, an anti-settling agent, etc. Is added to prepare a coating resin composition. Then, the said resin composition for coating
- the coating resin composition is an aqueous resin composition
- it is 70 ° C or higher, more preferably 90 ° C or higher, 150 ° C or lower, more preferably 120 ° C or lower.
- the temperature is 3 seconds or longer, more preferably 30 seconds or longer, 2 minutes or shorter, more preferably 1 minute or shorter.
- the drying temperature and drying time may be set according to the type of curing agent used.
- heat treatment may be performed simultaneously with the drying or after the drying to promote the resin component's curing reaction. This is the preferred mode.
- Measurement was performed by a laser diffraction method (dispersion method) using a Microtrack FRA9220 manufactured by Lead & Nrthrup.
- Weight loss Wd 3gZm 2 or more, X (Poor formability) Weight loss Wd: ⁇ 2gZm 2 or more and less than 3gZm 2 ⁇ (Strength better than X above)
- an alloyed hot-dip galvanized steel plate with an adhesion amount of 45 gZm 2 was used, and a non-chromate type surface treatment was applied using PPG Nupal.
- the amount of base coating was applied with barcode so that the intensity of P was 1 with fluorescent X-rays.
- Epokey 834 is a resin component, 38, 28 parts by mass of phosphorous iron
- a bar coater was selected so that the thickness of the resin layer was 1.8 to 8 ⁇ m, and the above-mentioned ground treatment was applied to alloying and melting.
- the coating was applied to a zinc-plated steel sheet, and the solvent was removed and the resin layer was cured at PMT 230 ° C in a continuous heating furnace to obtain a resin-coated metal sheet.
- Table 1 summarizes the particle size distribution of the conductive particles used and the evaluation results of the obtained resin-coated metal sheet.
- the resin-coated metal sheet satisfying the formulas (1) to (3) is excellent in peel resistance.
- the metal plates 10 to 12 and 22 to 24 were cases where the formula (3) was not satisfied, and the peel resistance was lowered.
- the metal plate 25 did not satisfy the formula (1), and the peel resistance and the corrosion resistance (red wrinkles were generated in 10 cycles of the VDA test fitting part) were lowered.
- the metal plate 26 did not satisfy the formula (2), and the volume average particle diameter was too large with respect to the film thickness t, so that the peel resistance was lowered.
- the resin-coated metal sheet satisfying the formulas (1) to (3) has a welding continuous spot performance of 1000 points or more, and does not generate red defects in 15 cycles of the VDA test joint section. Both corrosion resistance and corrosion resistance were good. Industrial applicability
- the resin-coated metal plate of the present invention is suitable as a weldable painted metal plate frequently used for steel plates for automobiles, home appliances and the like.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Laminated Bodies (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT0925805A AT502867A1 (de) | 2004-07-09 | 2005-07-07 | Harzbeschichtetes metallblech |
US11/568,931 US20080187743A1 (en) | 2004-07-09 | 2005-07-07 | Resin-Coated Metal Sheet |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004203890A JP3764465B2 (ja) | 2004-07-09 | 2004-07-09 | 樹脂被覆金属板およびその製造方法 |
JP2004-203890 | 2004-07-09 |
Publications (1)
Publication Number | Publication Date |
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WO2006006498A1 true WO2006006498A1 (ja) | 2006-01-19 |
Family
ID=35783842
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2005/012587 WO2006006498A1 (ja) | 2004-07-09 | 2005-07-07 | 樹脂被覆金属板 |
Country Status (6)
Country | Link |
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US (1) | US20080187743A1 (ja) |
JP (1) | JP3764465B2 (ja) |
KR (1) | KR20070024713A (ja) |
CN (1) | CN1960862A (ja) |
AT (1) | AT502867A1 (ja) |
WO (1) | WO2006006498A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101945566A (zh) * | 2007-03-23 | 2011-01-12 | 株式会社神户制钢所 | 导电性树脂涂敷金属板 |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4959283B2 (ja) * | 2006-05-09 | 2012-06-20 | エスケー化研株式会社 | 塗装方法 |
JP4949757B2 (ja) * | 2006-07-07 | 2012-06-13 | エスケー化研株式会社 | 下塗材組成物及びそれを用いた塗装方法 |
JP5036363B2 (ja) * | 2007-03-27 | 2012-09-26 | 株式会社神戸製鋼所 | 導電性樹脂塗装金属板 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63142072A (ja) * | 1986-12-03 | 1988-06-14 | Nippon Steel Chem Co Ltd | 塗装金属板 |
JPH11216420A (ja) * | 1998-02-03 | 1999-08-10 | Kobe Steel Ltd | 耐剥離性及び塗膜密着性に優れた溶接可能塗装金属板 |
JPH11302578A (ja) * | 1998-04-27 | 1999-11-02 | Toyo Ink Mfg Co Ltd | 塗装方法及び塗装品 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100363438C (zh) * | 2002-04-20 | 2008-01-23 | 坎梅陶尔股份有限公司 | 用于施涂耐腐蚀的、可电焊的聚合物涂层的混合物和用于生产该涂层的方法 |
-
2004
- 2004-07-09 JP JP2004203890A patent/JP3764465B2/ja not_active Expired - Fee Related
-
2005
- 2005-07-07 US US11/568,931 patent/US20080187743A1/en not_active Abandoned
- 2005-07-07 KR KR1020077000483A patent/KR20070024713A/ko not_active Application Discontinuation
- 2005-07-07 CN CNA2005800177335A patent/CN1960862A/zh active Pending
- 2005-07-07 WO PCT/JP2005/012587 patent/WO2006006498A1/ja active Application Filing
- 2005-07-07 AT AT0925805A patent/AT502867A1/de not_active Application Discontinuation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63142072A (ja) * | 1986-12-03 | 1988-06-14 | Nippon Steel Chem Co Ltd | 塗装金属板 |
JPH11216420A (ja) * | 1998-02-03 | 1999-08-10 | Kobe Steel Ltd | 耐剥離性及び塗膜密着性に優れた溶接可能塗装金属板 |
JPH11302578A (ja) * | 1998-04-27 | 1999-11-02 | Toyo Ink Mfg Co Ltd | 塗装方法及び塗装品 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101945566A (zh) * | 2007-03-23 | 2011-01-12 | 株式会社神户制钢所 | 导电性树脂涂敷金属板 |
Also Published As
Publication number | Publication date |
---|---|
JP2006021506A (ja) | 2006-01-26 |
AT502867A1 (de) | 2007-06-15 |
CN1960862A (zh) | 2007-05-09 |
US20080187743A1 (en) | 2008-08-07 |
JP3764465B2 (ja) | 2006-04-05 |
KR20070024713A (ko) | 2007-03-02 |
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