JP6469403B2 - Method for producing metal / resin composite structure - Google Patents
Method for producing metal / resin composite structure Download PDFInfo
- Publication number
- JP6469403B2 JP6469403B2 JP2014205010A JP2014205010A JP6469403B2 JP 6469403 B2 JP6469403 B2 JP 6469403B2 JP 2014205010 A JP2014205010 A JP 2014205010A JP 2014205010 A JP2014205010 A JP 2014205010A JP 6469403 B2 JP6469403 B2 JP 6469403B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- metal
- composite structure
- resin composite
- metal member
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229910052751 metal Inorganic materials 0.000 title claims description 275
- 239000000805 composite resin Substances 0.000 title claims description 105
- 239000002905 metal composite material Substances 0.000 title claims description 105
- 238000004519 manufacturing process Methods 0.000 title claims description 58
- 239000002184 metal Substances 0.000 claims description 170
- 229920005989 resin Polymers 0.000 claims description 133
- 239000011347 resin Substances 0.000 claims description 133
- 229920005992 thermoplastic resin Polymers 0.000 claims description 53
- 238000000034 method Methods 0.000 claims description 45
- 239000011342 resin composition Substances 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 238000011156 evaluation Methods 0.000 claims description 22
- 230000009477 glass transition Effects 0.000 claims description 21
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- 238000005520 cutting process Methods 0.000 claims description 15
- 238000002347 injection Methods 0.000 claims description 15
- 239000007924 injection Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 12
- 230000003746 surface roughness Effects 0.000 claims description 12
- 238000005304 joining Methods 0.000 claims description 11
- 229910000838 Al alloy Inorganic materials 0.000 claims description 8
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 8
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 8
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 8
- 229920006026 co-polymeric resin Polymers 0.000 claims description 6
- 239000002826 coolant Substances 0.000 claims description 6
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 5
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 5
- 229920005668 polycarbonate resin Polymers 0.000 claims description 5
- 239000004431 polycarbonate resin Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 230000005674 electromagnetic induction Effects 0.000 claims description 4
- 239000007769 metal material Substances 0.000 claims description 4
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 claims description 4
- 229920006350 polyacrylonitrile resin Polymers 0.000 claims description 4
- 229920005990 polystyrene resin Polymers 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 3
- 238000005530 etching Methods 0.000 description 52
- 239000003795 chemical substances by application Substances 0.000 description 42
- 239000002253 acid Substances 0.000 description 40
- 238000007788 roughening Methods 0.000 description 31
- 229910001447 ferric ion Inorganic materials 0.000 description 17
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 16
- 230000008569 process Effects 0.000 description 15
- 238000000465 moulding Methods 0.000 description 13
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 12
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 10
- 239000000945 filler Substances 0.000 description 10
- 238000001746 injection moulding Methods 0.000 description 10
- -1 polybutylene terephthalate Polymers 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 229910001437 manganese ion Inorganic materials 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000004734 Polyphenylene sulfide Substances 0.000 description 5
- 229920000069 polyphenylene sulfide Polymers 0.000 description 5
- 230000000630 rising effect Effects 0.000 description 5
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000000113 differential scanning calorimetry Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000000635 electron micrograph Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 229960003280 cupric chloride Drugs 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 229920002492 poly(sulfone) Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 229940099607 manganese chloride Drugs 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229920001643 poly(ether ketone) Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 229920000306 polymethylpentene Polymers 0.000 description 2
- 239000011116 polymethylpentene Substances 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920005497 Acrypet® Polymers 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 239000004801 Chlorinated PVC Substances 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 241000467686 Eschscholzia lobbii Species 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910021569 Manganese fluoride Inorganic materials 0.000 description 1
- 229920009204 Methacrylate-butadiene-styrene Polymers 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
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- 108010020346 Polyglutamic Acid Proteins 0.000 description 1
- 229920000331 Polyhydroxybutyrate Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920000491 Polyphenylsulfone Polymers 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000011354 acetal resin Substances 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
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- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
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- 210000000038 chest Anatomy 0.000 description 1
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- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013527 degreasing agent Substances 0.000 description 1
- 238000005237 degreasing agent Methods 0.000 description 1
- CTNMMTCXUUFYAP-UHFFFAOYSA-L difluoromanganese Chemical compound F[Mn]F CTNMMTCXUUFYAP-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
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- WOLATMHLPFJRGC-UHFFFAOYSA-N furan-2,5-dione;styrene Chemical compound O=C1OC(=O)C=C1.C=CC1=CC=CC=C1 WOLATMHLPFJRGC-UHFFFAOYSA-N 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
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- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
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- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
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- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
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- 238000013021 overheating Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
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- 239000003002 pH adjusting agent Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920011301 perfluoro alkoxyl alkane Polymers 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
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- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000010107 reaction injection moulding Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 210000003660 reticulum Anatomy 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 229920006259 thermoplastic polyimide Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/20—Acidic compositions for etching aluminium or alloys thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
- B29C45/14311—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles using means for bonding the coating to the articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2705/00—Use of metals, their alloys or their compounds, for preformed parts, e.g. for inserts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
Description
本発明は、金属／樹脂複合構造体の製造方法に関する。 The present invention relates to a method for producing a metal / resin composite structure.
各種部品の軽量化の観点から、金属の代替品として樹脂が使用されている。しかし、全ての金属部品を樹脂で代替することは難しい場合も多い。そのような場合には、金属成形体と樹脂成形体を接合一体化することで新たな複合部品を製造することが考えられる。しかしながら、金属成形体と樹脂成形体を工業的に有利な方法で、かつ高い接合強度で接合一体化できる技術は実用化されていない。 Resin is used as a substitute for metal from the viewpoint of weight reduction of various parts. However, it is often difficult to replace all metal parts with resin. In such a case, it is conceivable to manufacture a new composite part by joining and integrating the metal molded body and the resin molded body. However, a technique capable of joining and integrating a metal molded body and a resin molded body with an industrially advantageous method with high bonding strength has not been put into practical use.
近年、金属成形体と樹脂成形体を接合一体化する技術として、金属部材の表面に微細な凹凸を形成させたものに、その金属部材と親和性を有する極性基を持つエンジニアリングプラスチックを接合させることが検討されている（例えば、特許文献１〜５等）。 In recent years, as a technology for joining and integrating metal moldings and resin moldings, engineering plastics with polar groups that have affinity with the metal member are joined to the metal member surface with fine irregularities (For example, Patent Documents 1 to 5).
例えば、特許文献１〜３には、アルミニウム合金をヒドラジン水溶液で浸漬処理することによって、その表面に３０〜３００ｎｍ径の凹部を形成した後、該処理面にポリブチレンテレフタレート樹脂（以下「ＰＢＴ」という。）、またはポリフェニレンスルィド樹脂（以下「ＰＰＳ」という。）を接合させる技術が開示されている。 For example, in Patent Documents 1 to 3, after an aluminum alloy is immersed in a hydrazine aqueous solution to form a recess having a diameter of 30 to 300 nm on the surface, a polybutylene terephthalate resin (hereinafter referred to as “PBT”) is formed on the treated surface. ), Or a technique for joining a polyphenylene sulfide resin (hereinafter referred to as “PPS”).
また、特許文献４には、アルミニウム素材を燐酸または水酸化ナトリウムの電解浴で陽極酸化処理することにより、アルミニウム素材の表面に直径が２５ｎｍ以上である凹部を有する陽極酸化皮膜を形成した後、該処理面にエンジニアリングプラスチックを接合させる技術が開示されている。 In Patent Document 4, an aluminum material is anodized in an electrolytic bath of phosphoric acid or sodium hydroxide to form an anodized film having a recess having a diameter of 25 nm or more on the surface of the aluminum material, A technique for joining an engineering plastic to a processing surface is disclosed.
さらに、特許文献５には、アルミニウム合金に対し、特定のエッチング剤により微細な凹凸もしくは孔を形成し、その孔にポリアミド６樹脂、ポリアミド６６樹脂、ＰＰＳを射出接合させる技術が開示されている。 Further, Patent Document 5 discloses a technique in which fine irregularities or holes are formed in an aluminum alloy with a specific etching agent, and polyamide 6 resin, polyamide 66 resin, and PPS are injected and bonded to the holes.
本発明者らの検討によれば、特許文献１〜５に開示されているような方法で得られた金属／樹脂複合構造体の接合強度は、樹脂部材の種類や成形条件によって、接合強度が劣る場合があることが明らかになった。特に、樹脂部材として、非晶性熱可塑性樹脂を用いた場合に金属／樹脂複合構造体の接合強度に劣る場合が多いことが明らかになった。 According to the study by the present inventors, the bonding strength of the metal / resin composite structure obtained by the methods disclosed in Patent Documents 1 to 5 depends on the type of resin member and molding conditions. It became clear that it might be inferior. In particular, it has been clarified that when an amorphous thermoplastic resin is used as the resin member, the bonding strength of the metal / resin composite structure is often inferior.
本発明は上記事情に鑑みてなされたものであり、金属部材と、非晶性熱可塑性樹脂を含む樹脂組成物からなる樹脂部材との接合強度に優れた金属／樹脂複合構造体を安定的に、かつ、効率よく製造することが可能な金属／樹脂複合構造体の製造方法を提供するものである。 The present invention has been made in view of the above circumstances, and stably provides a metal / resin composite structure excellent in bonding strength between a metal member and a resin member made of a resin composition containing an amorphous thermoplastic resin. And the manufacturing method of the metal / resin composite structure which can be manufactured efficiently is provided.
本発明者らは、金属部材と、非晶性熱可塑性樹脂を含む樹脂組成物からなる樹脂部材との接合強度に優れた金属／樹脂複合構造体を安定的に、かつ、効率よく得るために、金属／樹脂複合構造体の成形条件を検討した。その結果、金型表面の温度プロファイルを特定のプロファイルに設定することで、接合強度に優れた金属／樹脂複合構造体を安定的に、かつ、効率よく得られることを見出し、本発明に到達した。 In order to stably and efficiently obtain a metal / resin composite structure excellent in bonding strength between a metal member and a resin member made of a resin composition containing an amorphous thermoplastic resin. The molding conditions of the metal / resin composite structure were examined. As a result, it was found that a metal / resin composite structure excellent in bonding strength can be obtained stably and efficiently by setting the temperature profile of the mold surface to a specific profile, and the present invention has been achieved. .
すなわち、本発明によれば、以下に示す金属／樹脂複合構造体の製造方法が提供される。 That is, according to this invention, the manufacturing method of the metal / resin composite structure shown below is provided.
［１］
金属部材と、非晶性熱可塑性樹脂を含む樹脂組成物からなる樹脂部材とが接合してなる金属／樹脂複合構造体を製造するための製造方法であって、
金型のキャビティ部に、間隔周期が５ｎｍ以上５００μｍ以下である凸部が林立した微細凹凸表面を有する上記金属部材を配置する工程と、
上記キャビティ部に上記樹脂組成物を射出することにより上記金属部材と上記樹脂部材とを接合する工程と、
を含み、
上記樹脂組成物の射出開始から保圧完了までの間、上記金型の表面温度を上記非晶性熱可塑性樹脂のガラス転移温度以上の温度に維持し、上記保圧完了後、上記金型の表面温度を上記非晶性熱可塑性樹脂のガラス転移温度未満の温度に冷却する金属／樹脂複合構造体の製造方法。
［２］
上記［１］に記載の金属／樹脂複合構造体の製造方法において、
上記金型の表面の近くに設けられた流路に水蒸気、温水および温油から選択される加熱媒体を導入する、あるいは電磁誘導加熱を用いることにより、上記金型の上記表面温度を上記非晶性熱可塑性樹脂のガラス転移温度以上の温度に維持する金属／樹脂複合構造体の製造方法。
［３］
上記［１］または［２］に記載の金属／樹脂複合構造体の製造方法において、
上記金型の表面の近くに設けられた流路に冷水および冷油から選択される冷却媒体を導入することにより、上記金型の上記表面温度を上記非晶性熱可塑性樹脂のガラス転移温度未満の温度に冷却する金属／樹脂複合構造体の製造方法。
［４］
上記［１］乃至［３］いずれか一つに記載の金属／樹脂複合構造体の製造方法において、
上記射出開始から上記保圧完了までの時間が１秒以上４０秒以下である金属／樹脂複合構造体の製造方法。
［５］
上記［１］乃至［４］いずれか一つに記載の金属／樹脂複合構造体の製造方法において、
上記非晶性熱可塑性樹脂が、ポリスチレン樹脂、ポリアクリロニトリル樹脂、スチレン−アクリロニトリル共重合体樹脂、アクリロニトリル−ブタジエン−スチレン共重合体樹脂、ポリメタクリル酸メチル樹脂、およびポリカーボネート樹脂から選択される一種または二種以上を含む金属／樹脂複合構造体の製造方法。
［６］
上記［１］乃至［５］いずれか一つに記載の金属／樹脂複合構造体の製造方法において、
上記金属部材の表面上の、平行関係にある任意の３直線部、および当該３直線部と直交する任意の３直線部からなる合計６直線部について、ＪＩＳ Ｂ０６０１（対応国際規格：ＩＳＯ４２８７）に準拠して測定される表面粗さが以下の要件（１）および（２）を同時に満たす金属／樹脂複合構造体の製造方法。
（１）切断レベル２０％、評価長さ４ｍｍにおける粗さ曲線の負荷長さ率（Ｒｍｒ）が３０％以下である直線部を１直線部以上含む
（２）すべての直線部の、評価長さ４ｍｍにおける十点平均粗さ（Ｒｚ）が２μｍを超える
［７］
上記［６］に記載の金属／樹脂複合構造体の製造方法において、
上記金属部材の表面上の、平行関係にある任意の３直線部、および当該３直線部と直交する任意の３直線部からなる合計６直線部について、ＪＩＳ Ｂ０６０１（対応国際規格：ＩＳＯ４２８７）に準拠して測定される表面粗さが以下の要件（３）をさらに満たす金属／樹脂複合構造体の製造方法。
（３）切断レベル４０％、評価長さ４ｍｍにおける粗さ曲線の負荷長さ率（Ｒｍｒ）が６０％以下である直線部を１直線部以上含む
［８］
上記［６］または［７］に記載の金属／樹脂複合構造体の製造方法において、
上記金属部材の表面上の、平行関係にある任意の３直線部、および当該３直線部と直交する任意の３直線部からなる合計６直線部について、すべての直線部の上記十点平均粗さ（Ｒｚ）が５μｍを超える金属／樹脂複合構造体の製造方法。
［９］
上記［８］に記載の金属／樹脂複合構造体の製造方法において、
上記金属部材の表面上の、平行関係にある任意の３直線部、および当該３直線部と直交する任意の３直線部からなる合計６直線部について、すべての直線部の上記十点平均粗さ（Ｒｚ）が１５μｍ以上である金属／樹脂複合構造体の製造方法。
［１０］
上記［１］乃至［９］いずれか一つに記載の金属／樹脂複合構造体の製造方法において、
上記金属部材はアルミニウムおよびアルミニウム合金から選択される一種または二種以上の金属を含む金属材料からなる金属／樹脂複合構造体の製造方法。
［１１］
上記［１］乃至［１０］いずれか一つに記載の金属／樹脂複合構造体の製造方法において、
上記非晶性熱可塑性樹脂のガラス転移温度をＴｇとしたとき、
上記樹脂組成物の上記射出開始から上記保圧完了までの間、上記金型の上記表面温度を上記非晶性熱可塑性樹脂のＴｇ＋（５以上１００以下）℃以上の温度に維持し、上記保圧完了後、上記金型の上記表面温度を上記非晶性熱可塑性樹脂のＴｇ−（５以上１００以下）℃以下の温度に冷却する金属／樹脂複合構造体の製造方法。
[1]
A manufacturing method for manufacturing a metal / resin composite structure formed by joining a metal member and a resin member made of a resin composition containing an amorphous thermoplastic resin,
A step of disposing the metal member having a fine concavo-convex surface in which convex portions having an interval period of 5 nm or more and 500 μm or less are formed in a cavity portion of a mold;
Bonding the metal member and the resin member by injecting the resin composition into the cavity portion;
Including
The surface temperature of the mold is maintained at a temperature equal to or higher than the glass transition temperature of the amorphous thermoplastic resin from the start of injection of the resin composition to the completion of pressure holding. A method for producing a metal / resin composite structure, wherein the surface temperature is cooled to a temperature lower than the glass transition temperature of the amorphous thermoplastic resin.
[2]
In the method for producing a metal / resin composite structure according to [1] above,
By introducing a heating medium selected from water vapor, hot water and hot oil into a flow path provided near the surface of the mold, or by using electromagnetic induction heating, the surface temperature of the mold is changed to the amorphous state. For producing a metal / resin composite structure, which is maintained at a temperature equal to or higher than the glass transition temperature of the thermoplastic resin.
[3]
In the method for producing a metal / resin composite structure according to [1] or [2] above,
By introducing a cooling medium selected from cold water and cold oil into a flow path provided near the surface of the mold, the surface temperature of the mold is less than the glass transition temperature of the amorphous thermoplastic resin. The manufacturing method of the metal / resin composite structure cooled to the temperature of this.
[4]
In the method for producing a metal / resin composite structure according to any one of [1] to [3] above,
A method for producing a metal / resin composite structure, wherein the time from the start of injection to the completion of pressure holding is from 1 second to 40 seconds.
[5]
In the method for producing a metal / resin composite structure according to any one of [1] to [4] above,
The amorphous thermoplastic resin is one or two selected from polystyrene resin, polyacrylonitrile resin, styrene-acrylonitrile copolymer resin, acrylonitrile-butadiene-styrene copolymer resin, polymethyl methacrylate resin, and polycarbonate resin. A method for producing a metal / resin composite structure containing more than one species.
[6]
In the method for producing a metal / resin composite structure according to any one of [1] to [5] above,
Conforms to JIS B0601 (corresponding international standard: ISO4287) for a total of 6 straight line parts consisting of any 3 straight line parts in parallel relation on the surface of the metal member and any 3 straight line parts orthogonal to the 3 straight line parts A method for producing a metal / resin composite structure in which the measured surface roughness satisfies the following requirements (1) and (2) simultaneously.
(1) Includes one or more straight line portions with a load length ratio (Rmr) of a roughness curve at a cutting level of 20% and an evaluation length of 4 mm of 30% or less. (2) Evaluation length of all straight line portions. Ten point average roughness (Rz) at 4 mm exceeds 2 μm [7]
In the method for producing a metal / resin composite structure according to [6] above,
Conforms to JIS B0601 (corresponding international standard: ISO4287) for a total of 6 straight line parts consisting of any 3 straight line parts in parallel relation on the surface of the metal member and any 3 straight line parts orthogonal to the 3 straight line parts A method for producing a metal / resin composite structure, wherein the surface roughness measured by the method further satisfies the following requirement (3).
(3) One or more straight line parts having a load length ratio (Rmr) of a roughness curve at a cutting level of 40% and an evaluation length of 4 mm are 60% or less [8]
In the method for producing a metal / resin composite structure according to [6] or [7] above,
The above-mentioned ten-point average roughness of all the straight portions of a total of six straight portions composed of any three straight portions in parallel relation on the surface of the metal member and any three straight portions orthogonal to the three straight portions. A method for producing a metal / resin composite structure in which (Rz) exceeds 5 μm.
[9]
In the method for producing a metal / resin composite structure according to [8] above,
The above-mentioned ten-point average roughness of all the straight portions of a total of six straight portions composed of any three straight portions in parallel relation on the surface of the metal member and any three straight portions orthogonal to the three straight portions. A method for producing a metal / resin composite structure, wherein (Rz) is 15 μm or more.
[10]
In the method for producing a metal / resin composite structure according to any one of [1] to [9] above,
The said metal member is a manufacturing method of the metal / resin composite structure which consists of a metal material containing the 1 type, or 2 or more types of metal selected from aluminum and aluminum alloy.
[11]
In the method for producing a metal / resin composite structure according to any one of [1] to [10] above,
When the glass transition temperature of the amorphous thermoplastic resin is Tg,
During the period from the start of injection of the resin composition to the completion of the pressure holding, the surface temperature of the mold is maintained at a temperature equal to or higher than Tg + (5 to 100) ° C of the amorphous thermoplastic resin. A method for producing a metal / resin composite structure, wherein the surface temperature of the mold is cooled to a temperature of Tg− (5 to 100) ° C. of the amorphous thermoplastic resin after completion of the pressing.
本発明によれば、金属部材と、非晶性熱可塑性樹脂を含む樹脂組成物からなる樹脂部材との接合強度に優れた金属／樹脂複合構造体を安定的に、かつ、効率よく製造することが可能な金属／樹脂複合構造体の製造方法を提供することができる。 According to the present invention, a metal / resin composite structure excellent in bonding strength between a metal member and a resin member comprising a resin composition containing an amorphous thermoplastic resin can be stably and efficiently produced. It is possible to provide a method for producing a metal / resin composite structure that can be used.
以下に、本発明の実施形態について、図面を用いて説明する。なお、すべての図面において、同様な構成要素には共通の符号を付し、適宜説明を省略する。なお、文中の数字の間にある「〜」は特に断りがなければ、以上から以下を表す。 Embodiments of the present invention will be described below with reference to the drawings. In all the drawings, similar constituent elements are denoted by common reference numerals, and description thereof is omitted as appropriate. In addition, "-" between the numbers in a sentence represents the following from the above, unless there is particular notice.
［金属／樹脂複合構造体］
まず、本実施形態に係る金属／樹脂複合構造体１０６について説明する。
図１は、本発明に係る実施形態の金属／樹脂複合構造体１０６の構造の一例を模式的に示した外観図である。金属／樹脂複合構造体１０６は、金属部材１０３と、非晶性熱可塑性樹脂（Ａ）を含む樹脂組成物（Ｐ）からなる樹脂部材１０５とが接合されており、金属部材１０３と樹脂部材１０５とを接合することにより得られる。
本実施形態に係る金属／樹脂複合構造体１０６は、樹脂部材１０５を構成する樹脂組成物（Ｐ）が、金属部材１０３の表面１１０に形成された間隔周期が５ｎｍ以上５００μｍ以下である凸部が林立した微細凹凸に侵入して金属と樹脂が接合し、金属―樹脂界面を形成することにより得られる。
[Metal / resin composite structure]
First, the metal / resin composite structure 106 according to the present embodiment will be described.
FIG. 1 is an external view schematically showing an example of the structure of the metal / resin composite structure 106 according to the embodiment of the present invention. In the metal / resin composite structure 106, a metal member 103 and a resin member 105 made of a resin composition (P) containing an amorphous thermoplastic resin (A) are joined, and the metal member 103 and the resin member 105 are joined together. It is obtained by joining together.
In the metal / resin composite structure 106 according to the present embodiment, the resin composition (P) constituting the resin member 105 has protrusions having a spacing period of 5 nm or more and 500 μm or less formed on the surface 110 of the metal member 103. It is obtained by intruding into the forested fine irregularities and joining the metal and resin to form a metal-resin interface.
金属部材１０３の表面１１０には、金属部材１０３と樹脂部材１０５との間の接合強度向上に適した微細凹凸形状が形成されているため、接着剤を使用せずに金属部材１０３と樹脂部材１０５との間の接合性確保が可能となる。
具体的には金属部材１０３の表面１１０の上記微細凹凸形状の中に樹脂組成物（Ｐ）が侵入することによって、金属部材１０３と樹脂部材１０５との間に物理的な抵抗力（アンカー効果）が効果的に発現し、通常では接合が困難な金属部材１０３と樹脂組成物（Ｐ）からなる樹脂部材１０５とを強固に接合することが可能になる。
Since the surface 110 of the metal member 103 has a fine concavo-convex shape suitable for improving the bonding strength between the metal member 103 and the resin member 105, the metal member 103 and the resin member 105 can be used without using an adhesive. Can be secured.
Specifically, the physical resistance (anchor effect) between the metal member 103 and the resin member 105 due to the penetration of the resin composition (P) into the fine uneven shape of the surface 110 of the metal member 103. Can be effectively bonded, and the metal member 103, which is normally difficult to bond, and the resin member 105 made of the resin composition (P) can be firmly bonded.
このようにして得られた金属／樹脂複合構造体１０６は、金属部材１０３と樹脂部材１０５の界面への水分や湿気の浸入を防ぐこともできる。つまり、金属／樹脂複合構造体１０６の付着界面における気密性や水密性を向上させることもできる。
以下、金属／樹脂複合構造体１０６を構成する各部材について説明する。
The metal / resin composite structure 106 obtained in this manner can also prevent moisture and moisture from entering the interface between the metal member 103 and the resin member 105. That is, the air tightness and water tightness at the adhesion interface of the metal / resin composite structure 106 can be improved.
Hereinafter, each member constituting the metal / resin composite structure 106 will be described.
＜金属部材＞
以下、本実施形態に係る金属部材１０３について説明する。
本実施形態に係る金属部材１０３は、間隔周期が５ｎｍ以上５００μｍ以下である凸部が林立した微細凹凸表面を有する。
上記微細凹凸表面の間隔周期は凸部から隣接する凸部までの距離の平均値であり、電子顕微鏡またはレーザー顕微鏡で撮影した写真から求めることができる。
具体的には、電子顕微鏡またはレーザー顕微鏡により、金属部材１０３の表面１１０を撮影する。その写真から、任意の凸部を５０個選択し、それらの凸部から隣接する凸部までの距離をそれぞれ測定する。凸部から隣接する凸部までの距離の全てを積算して５０で除したものを間隔周期とする。
<Metal member>
Hereinafter, the metal member 103 according to the present embodiment will be described.
The metal member 103 according to the present embodiment has a fine concavo-convex surface in which convex portions having an interval period of 5 nm or more and 500 μm or less stand.
The interval period of the surface of the fine unevenness is an average value of the distance from the convex portion to the adjacent convex portion, and can be obtained from a photograph taken with an electron microscope or a laser microscope.
Specifically, the surface 110 of the metal member 103 is photographed with an electron microscope or a laser microscope. From the photograph, 50 arbitrary convex portions are selected, and the distances from those convex portions to adjacent convex portions are measured. An interval period is defined by integrating all the distances from the convex portion to the adjacent convex portion and dividing the sum by 50.
凸部の間隔周期は、好ましくは１０ｎｍ以上３００μｍ以下、より好ましくは２０ｎｍ以上２００μｍ以下である。
凸部の間隔周期が上記下限値以上であると、上記微細凹凸表面の凹部に非晶性熱可塑性樹脂（Ａ）が十分に進入することができ、金属部材１０３と樹脂部材１０５との接合強度をより向上させることができる。また、凸部の間隔周期が上記上限値以下であると、得られる金属／樹脂複合構造体１０６の金属―樹脂界面に隙間が生じるのを抑制できる。その結果、金属―樹脂界面の隙間から水分等の不純物が浸入することが抑制できるため、金属／樹脂複合構造体１０６を高温、高湿下で用いた際、強度が低下することを抑制できる。
The interval period of the convex portions is preferably 10 nm or more and 300 μm or less, more preferably 20 nm or more and 200 μm or less.
When the interval interval of the protrusions is equal to or more than the lower limit value, the amorphous thermoplastic resin (A) can sufficiently enter the recesses on the surface of the fine unevenness, and the bonding strength between the metal member 103 and the resin member 105 is increased. Can be further improved. Moreover, when the interval period of the convex portions is equal to or less than the above upper limit value, it is possible to suppress the generation of a gap at the metal-resin interface of the obtained metal / resin composite structure 106. As a result, it is possible to suppress the intrusion of impurities such as moisture from the gap between the metal-resin interface, and thus it is possible to suppress a decrease in strength when the metal / resin composite structure 106 is used at high temperature and high humidity.
上記間隔周期を有する微細凹凸表面を形成する方法としては、ＮａＯＨ等の無機塩基水溶液および／またはＨＣｌ、ＨＮＯ３等の無機酸水溶液に金属部材を浸漬する方法、陽極酸化法により金属部材を処理する方法、国際公開第２００９／３１６３２号パンフレットに開示されているような、水和ヒドラジン、アンモニア、及び水溶性アミン化合物から選ばれる１種以上の水溶液に金属部材を浸漬する方法などが挙げられる。これらの方法は、使用する金属部材１０３の金属種類や、上記間隔周期の範囲内において形成する凹凸形状によって使い分けることが可能である。 As a method of forming a fine uneven surface having the above-mentioned interval cycle, a metal member is treated by an inorganic base aqueous solution such as NaOH and / or a metal member immersed in an inorganic acid aqueous solution such as HCl or HNO 3, or an anodic oxidation method. And a method of immersing a metal member in one or more aqueous solutions selected from hydrated hydrazine, ammonia, and a water-soluble amine compound as disclosed in WO 2009/31632 pamphlet. These methods can be properly used depending on the metal type of the metal member 103 to be used and the uneven shape formed within the interval period.
本実施形態に係る金属部材１０３は、金属部材１０３の表面１１０上の、平行関係にある任意の３直線部、および当該３直線部と直交する任意の３直線部からなる合計６直線部について、ＪＩＳ Ｂ０６０１（対応国際規格：ＩＳＯ４２８７）に準拠して測定される表面粗さが以下の要件（１）および（２）を同時に満たすことが好ましい。
（１）切断レベル２０％、評価長さ４ｍｍにおける粗さ曲線の負荷長さ率（Ｒｍｒ）が３０％以下である直線部を１直線部以上含む
（２）すべての直線部の、評価長さ４ｍｍにおける十点平均粗さ（Ｒｚ）が２μｍを超える
The metal member 103 according to the present embodiment has a total of six linear portions including arbitrary three linear portions in parallel relation on the surface 110 of the metal member 103 and arbitrary three linear portions orthogonal to the three linear portions. It is preferable that the surface roughness measured according to JIS B0601 (corresponding international standard: ISO4287) satisfies the following requirements (1) and (2) simultaneously.
(1) Includes one or more straight line portions with a load length ratio (Rmr) of a roughness curve at a cutting level of 20% and an evaluation length of 4 mm of 30% or less. (2) Evaluation length of all straight line portions. Ten point average roughness (Rz) at 4 mm exceeds 2 μm
図３は、金属部材１０３の表面１１０上の、平行関係にある任意の３直線部、および当該３直線部と直交する任意の３直線部からなる合計６直線部を説明するための模式図である。
上記６直線部は、例えば、図３に示すような６直線部Ｂ１〜Ｂ６を選択することができる。まず、基準線として、金属部材１０３の接合部表面１０４の中心部Ａを通る中心線Ｂ１を選択する。次いで、中心線Ｂ１と平行関係にある直線Ｂ２およびＢ３を選択する。次いで、中心線Ｂ１と直交する中心線Ｂ４を選択し、中心線Ｂ１と直交し、中心線Ｂ４と並行関係にある直線Ｂ５およびＢ６を選択する。ここで、各直線間の垂直距離Ｄ１〜Ｄ４は、例えば、２〜５ｍｍである。
なお、通常、金属部材の表面１１０中の接合部表面１０４だけでなく、金属部材の表面１１０全体に対し、表面粗化処理が施されているため、例えば、図４に示すように、金属部材１０３の接合部表面１０４と同一面で、接合部表面１０４以外の箇所から６直線部を選択してもよい。
FIG. 3 is a schematic diagram for explaining a total of six linear portions including arbitrary three linear portions in parallel relation on the surface 110 of the metal member 103 and arbitrary three linear portions orthogonal to the three linear portions. is there.
As the six straight line portions, for example, six straight line portions B1 to B6 as shown in FIG. 3 can be selected. First, a center line B1 passing through the center portion A of the joint surface 104 of the metal member 103 is selected as the reference line. Next, straight lines B2 and B3 that are parallel to the center line B1 are selected. Next, a center line B4 orthogonal to the center line B1 is selected, and straight lines B5 and B6 orthogonal to the center line B1 and parallel to the center line B4 are selected. Here, the vertical distances D1 to D4 between the straight lines are, for example, 2 to 5 mm.
In addition, since the surface roughening process is normally performed not only on the joint surface 104 in the surface 110 of the metal member but also on the entire surface 110 of the metal member, for example, as shown in FIG. The six straight line portions may be selected from locations other than the joint surface 104 on the same plane as the joint surface 104 of 103.
上記要件（１）および（２）を同時に満たすと、接合強度により一層優れた金属／樹脂複合構造体１０６が得られる理由は必ずしも明らかではないが、金属部材１０３の接合部表面１０４が、金属部材１０３と樹脂部材１０５との間のアンカー効果が効果的に発現できる構造になっているためと考えられる。
本発明者らは、金属部材と、非晶性熱可塑性樹脂を含む樹脂組成物からなる樹脂部材との接合強度を向上させるために、金属部材の表面の十点平均粗さ（Ｒｚ）を調整することを検討した。
しかし、金属部材の表面の十点平均粗さ（Ｒｚ）を単に調整するだけでは金属部材と樹脂部材との接合強度を十分に向上させることができないことが明らかとなった。
ここで、本発明者らは、負荷長さ率という尺度が金属部材表面の凹凸形状の鋭利性を表す指標として有効であると考えた。負荷長さ率が小さい場合は、金属部材表面の凹凸形状の鋭利性が大きいことを意味し、負荷長さ率が大きい場合は、金属部材表面の凹凸形状の鋭利性が小さいことを意味する。
そこで、本発明者らは、金属部材と、非晶性熱可塑性樹脂を含む樹脂組成物からなる樹脂部材との接合強度を向上させるための設計指針として、金属部材表面の粗さ曲線の負荷長さ率という尺度に注目し、さらに鋭意検討を重ねた。その結果、金属部材表面の負荷長さ率を特定値以下に調整することにより、金属部材１０３と樹脂部材１０５との間にアンカー効果がより効果的に発現し、その結果、接合強度により一層優れた金属／樹脂複合構造体１０６が実現できることを見出した。
When the above requirements (1) and (2) are satisfied at the same time, it is not always clear why the metal / resin composite structure 106 having better bonding strength can be obtained. This is probably because the anchor effect between 103 and the resin member 105 can be effectively expressed.
The inventors adjust the ten-point average roughness (Rz) of the surface of the metal member in order to improve the bonding strength between the metal member and the resin member made of the resin composition containing the amorphous thermoplastic resin. Considered to do.
However, it has been clarified that the bonding strength between the metal member and the resin member cannot be sufficiently improved by simply adjusting the ten-point average roughness (Rz) of the surface of the metal member.
Here, the present inventors considered that the scale of the load length ratio is effective as an index representing the sharpness of the uneven shape on the surface of the metal member. When the load length rate is small, it means that the sharpness of the uneven shape on the surface of the metal member is large, and when the load length rate is large, it means that the sharpness of the uneven shape on the surface of the metal member is small.
Therefore, the present inventors have applied the load length of the roughness curve of the surface of the metal member as a design guide for improving the bonding strength between the metal member and the resin member made of the resin composition containing the amorphous thermoplastic resin. We paid attention to the scale of depth and conducted further diligent studies. As a result, by adjusting the load length ratio of the metal member surface to a specific value or less, the anchor effect is more effectively expressed between the metal member 103 and the resin member 105, and as a result, the joint strength is further improved. It has been found that a metal / resin composite structure 106 can be realized.
金属部材１０３と樹脂部材１０５との接合強度をより一層向上させる観点から、金属部材１０３の表面１１０上の、平行関係にある任意の３直線部、および当該３直線部と直交する任意の３直線部からなる合計６直線部について、ＪＩＳ Ｂ０６０１（対応国際規格：ＩＳＯ４２８７）に準拠して測定される表面粗さが以下の要件（１Ａ）〜（１Ｃ）のうち１つ以上の要件をさらに満たすことが好ましく、要件（１Ｃ）を満たすことがとりわけ好ましい。なお、要件（１Ｃ）は上述した要件（３）と同一である。
（１Ａ）切断レベル２０％、評価長さ４ｍｍにおける粗さ曲線の負荷長さ率（Ｒｍｒ）が３０％以下である直線部を好ましくは２直線部以上、より好ましくは３直線部以上、最も好ましくは６直線部含む
（１Ｂ）切断レベル２０％、評価長さ４ｍｍにおける粗さ曲線の負荷長さ率（Ｒｍｒ）が２０％以下である直線部を好ましくは１直線部以上、より好ましくは２直線部以上、さらに好ましくは３直線部以上、最も好ましくは６直線部含む
（１Ｃ）切断レベル４０％、評価長さ４ｍｍにおける粗さ曲線の負荷長さ率（Ｒｍｒ）が６０％以下である直線部を好ましくは１直線部以上、より好ましくは２直線部以上、さらに好ましくは３直線部以上、最も好ましくは６直線部含む
From the viewpoint of further improving the bonding strength between the metal member 103 and the resin member 105, any three straight lines in a parallel relationship on the surface 110 of the metal member 103 and any three straight lines orthogonal to the three straight lines. The surface roughness measured in accordance with JIS B0601 (corresponding international standard: ISO4287) further satisfies one or more of the following requirements (1A) to (1C) for a total of 6 straight line parts composed of parts. It is particularly preferable that the requirement (1C) is satisfied. The requirement (1C) is the same as the requirement (3) described above.
(1A) A straight line portion with a load length ratio (Rmr) of a roughness curve at a cutting level of 20% and an evaluation length of 4 mm is preferably 30% or less, preferably 2 straight portions or more, more preferably 3 straight portions or more, most preferably (1B) A straight line portion having a load length ratio (Rmr) of a roughness curve at a cutting level of 20% and an evaluation length of 4 mm is preferably 20% or less, preferably 1 straight line portion or more, more preferably 2 straight lines. Part or more, more preferably 3 straight parts or more, most preferably 6 straight parts are included. (1C) Straight line part having a load length ratio (Rmr) of 60% or less of the roughness curve at a cutting level of 40% and an evaluation length of 4 mm Is preferably 1 straight part or more, more preferably 2 straight parts or more, further preferably 3 straight parts or more, and most preferably 6 straight parts
また、金属部材１０３と樹脂部材１０５との接合強度をより一層向上させる観点から、金属部材１０３の表面１１０上の、ＪＩＳ Ｂ０６０１（対応国際規格：ＩＳＯ４２８７）に準拠して測定される切断レベル２０％、評価長さ４ｍｍにおける粗さ曲線の負荷長さ率（Ｒｍｒ）の平均値が好ましくは０．１％以上４０％以下であり、より好ましくは０．５％以上３０％以下であり、さらに好ましくは１％以上２０％以下であり、最も好ましくは２％以上１５％以下である。
なお、上記負荷長さ率（Ｒｍｒ）の平均値は、前述の任意の６直線部の負荷長さ率（Ｒｍｒ）を平均したものを採用することができる。
Further, from the viewpoint of further improving the bonding strength between the metal member 103 and the resin member 105, a cutting level of 20% measured on the surface 110 of the metal member 103 in accordance with JIS B0601 (corresponding international standard: ISO 4287). The average value of the load length ratio (Rmr) of the roughness curve at an evaluation length of 4 mm is preferably 0.1% or more and 40% or less, more preferably 0.5% or more and 30% or less, and still more preferably. Is from 1% to 20%, and most preferably from 2% to 15%.
In addition, what averaged the load length rate (Rmr) of the above-mentioned arbitrary 6 linear parts can be employ | adopted for the average value of the said load length rate (Rmr).
本実施形態に係る金属部材１０３の表面１１０の各負荷長さ率（Ｒｍｒ）は、金属部材１０３の表面に対する粗化処理の条件を適切に調節することにより制御することが可能である。
本実施形態においては、とくにエッチング剤の種類および濃度、粗化処理の温度および時間、エッチング処理のタイミング等が、上記各負荷長さ率（Ｒｍｒ）を制御するための因子として挙げられる。
Each load length ratio (Rmr) of the surface 110 of the metal member 103 according to the present embodiment can be controlled by appropriately adjusting the conditions of the roughening treatment on the surface of the metal member 103.
In the present embodiment, the type and concentration of the etching agent, the temperature and time of the roughening treatment, the timing of the etching treatment, and the like are particularly cited as factors for controlling the load length ratios (Rmr).
金属部材１０３と樹脂部材１０５との接合強度をより一層向上させる観点から、金属部材１０３の表面１１０上の、平行関係にある任意の３直線部、および当該３直線部と直交する任意の３直線部からなる合計６直線部について、ＪＩＳ Ｂ０６０１（対応国際規格：ＩＳＯ４２８７）に準拠して測定される表面粗さが以下の要件（２Ａ）をさらに満たすことが好ましい。
（２Ａ）すべての直線部の、評価長さ４ｍｍにおける十点平均粗さ（Ｒｚ）が好ましくは５μｍ超、より好ましくは１０μｍ以上、さらに好ましくは１５μｍ以上である
From the viewpoint of further improving the bonding strength between the metal member 103 and the resin member 105, any three straight lines in a parallel relationship on the surface 110 of the metal member 103 and any three straight lines orthogonal to the three straight lines. It is preferable that the surface roughness measured in accordance with JIS B0601 (corresponding international standard: ISO4287) further satisfies the following requirement (2A) for a total of six straight line parts composed of parts.
(2A) The 10-point average roughness (Rz) at an evaluation length of 4 mm of all straight portions is preferably more than 5 μm, more preferably 10 μm or more, and further preferably 15 μm or more.
金属部材１０３と樹脂部材１０５との接合強度をより一層向上させる観点から、金属部材１０３の表面１１０上の、十点平均粗さ（Ｒｚ）の平均値が好ましくは２μｍを超えて５０μｍ以下、より好ましくは５μｍを超えて４５μｍ以下、さらに好ましくは１０μｍ以上４０μｍ以下、特に好ましくは１５μｍ以上３０μｍ以下である。
なお、上記十点平均粗さ（Ｒｚ）の平均値は、前述の任意の６直線部の十点平均粗さ（Ｒｚ）を平均したものを採用することができる。
From the viewpoint of further improving the bonding strength between the metal member 103 and the resin member 105, the average value of the ten-point average roughness (Rz) on the surface 110 of the metal member 103 is preferably more than 2 μm and 50 μm or less, and more The thickness is preferably more than 5 μm and 45 μm or less, more preferably 10 μm or more and 40 μm or less, and particularly preferably 15 μm or more and 30 μm or less.
In addition, what averaged the 10-point average roughness (Rz) of the above-mentioned arbitrary 6 linear parts can be employ | adopted for the average value of the said 10-point average roughness (Rz).
金属部材１０３と樹脂部材１０５との接合強度をより一層向上させる観点から、金属部材１０３の表面１１０上の、平行関係にある任意の３直線部、および当該３直線部と直交する任意の３直線部からなる合計６直線部について、ＪＩＳ Ｂ０６０１（対応国際規格：ＩＳＯ４２８７）に準拠して測定される表面粗さが以下の要件（４）をさらに満たすことが好ましい。
（４）すべての直線部の、粗さ曲線要素の平均長さ（ＲＳｍ）が１０μｍを超え３００μｍ未満であり、より好ましくは２０μｍ以上２００μｍ以下である。
From the viewpoint of further improving the bonding strength between the metal member 103 and the resin member 105, any three straight lines in a parallel relationship on the surface 110 of the metal member 103 and any three straight lines orthogonal to the three straight lines. It is preferable that the surface roughness measured in accordance with JIS B0601 (corresponding international standard: ISO4287) further satisfies the following requirement (4) for a total of six straight line parts composed of parts.
(4) The average length (RSm) of the roughness curve elements of all the linear portions is more than 10 μm and less than 300 μm, more preferably 20 μm or more and 200 μm or less.
金属部材１０３と樹脂部材１０５との接合強度をより一層向上させる観点から、金属部材１０３の表面１１０上の、粗さ曲線要素の平均長さ（ＲＳｍ）の平均値が好ましくは１０μｍを超え３００μｍ未満、より好ましくは２０μｍ以上２００μｍ以下である。
なお、上記粗さ曲線要素の平均長さ（ＲＳｍ）の平均値は、前述の任意の６直線部のＲＳｍを平均したものを採用することができる。
From the viewpoint of further improving the bonding strength between the metal member 103 and the resin member 105, the average value of the average length (RSm) of the roughness curve elements on the surface 110 of the metal member 103 is preferably more than 10 μm and less than 300 μm. More preferably, it is 20 μm or more and 200 μm or less.
In addition, what averaged RSm of the above-mentioned arbitrary 6 linear parts can be employ | adopted for the average value of the average length (RSm) of the said roughness curve element.
本実施形態に係る金属部材１０３の表面１１０の十点平均粗さ（Ｒｚ）および粗さ曲線要素の平均長さ（ＲＳｍ）は、金属部材１０３の表面１１０に対する粗化処理の条件を適切に調節することにより制御することが可能である。
本実施形態においては、とくに粗化処理の温度および時間、エッチング量等が、上記十点平均粗さ（Ｒｚ）および粗さ曲線要素の平均長さ（ＲＳｍ）を制御するための因子として挙げられる。
The ten-point average roughness (Rz) of the surface 110 of the metal member 103 and the average length (RSm) of the roughness curve element according to the present embodiment appropriately adjust the conditions of the roughening treatment for the surface 110 of the metal member 103. It is possible to control by doing.
In the present embodiment, the temperature and time of the roughening treatment, the etching amount, etc. are particularly cited as factors for controlling the ten-point average roughness (Rz) and the average length (RSm) of the roughness curve elements. .
金属部材１０３を構成する金属材料は特に限定されないが、例えば、鉄、ステンレス、アルミニウム、アルミニウム合金、マグネシウム、マグネシウム合金、銅および銅合金等を挙げることができる。これらは単独で使用してもよいし、二種以上組み合わせて使用してもよい。これらの中でも、軽量かつ高強度の点から、アルミニウム（アルミニウム単体）およびアルミニウム合金が好ましく、アルミニウム合金がより好ましい。
アルミニウム合金としては、ＪＩＳ Ｈ４０００に規定された合金番号１０５０、１１００、２０１４、２０２４、３００３、５０５２、６０６１、６０６３、７０７５等が好ましく用いられる。
Although the metal material which comprises the metal member 103 is not specifically limited, For example, iron, stainless steel, aluminum, an aluminum alloy, magnesium, a magnesium alloy, copper, a copper alloy, etc. can be mentioned. These may be used alone or in combination of two or more. Among these, aluminum (aluminum simple substance) and aluminum alloy are preferable from the viewpoint of light weight and high strength, and aluminum alloy is more preferable.
As the aluminum alloy, alloy numbers 1050, 1100, 2014, 2024, 3003, 5052, 6061, 6063, and 7075 defined in JIS H4000 are preferably used.
金属部材１０３の形状は、樹脂部材１０５と接合できる形状であれば特に限定されず、例えば、平板状、曲板状、棒状、筒状、塊状等とすることができる。また、これらの組み合わせからなる構造体であってもよい。
また、樹脂部材１０５と接合する接合部表面１０４の形状は、特に限定されないが、平面、曲面等が挙げられる。
The shape of the metal member 103 is not particularly limited as long as it can be joined to the resin member 105. For example, the metal member 103 can have a flat plate shape, a curved plate shape, a rod shape, a cylindrical shape, a lump shape, or the like. Moreover, the structure which consists of these combination may be sufficient.
Further, the shape of the joint surface 104 to be joined to the resin member 105 is not particularly limited, and examples thereof include a flat surface and a curved surface.
金属部材１０３は、金属材料を切断、プレス等による塑性加工、打ち抜き加工、切削、研磨、放電加工等の除肉加工によって上述した所定の形状に加工された後に、後述する粗化処理がなされたものが好ましい。要するに、種々の加工法により、必要な形状に加工されたものを用いることが好ましい。
必要な形状に加工された金属部材１０３は、樹脂組成物（Ｐ）と接合する面が酸化や水酸化されていないことが好ましく、長期間の自然放置で表面に酸化皮膜である錆の存在が明らかなものは研磨、化学処理等でこれを取り除くことが好ましい。
The metal member 103 was processed into a predetermined shape as described above by metal removal such as cutting, pressing, etc., metal processing, punching, cutting, polishing, electric discharge processing, etc., and then the roughening process described later was performed. Those are preferred. In short, it is preferable to use a material processed into a necessary shape by various processing methods.
The surface of the metal member 103 processed into the required shape is preferably not oxidized or hydroxylated on the surface to be bonded to the resin composition (P), and the presence of rust which is an oxide film on the surface when left standing for a long period of time. What is obvious is preferably removed by polishing, chemical treatment or the like.
次に、上記要件（１）〜（４）、（１Ａ）〜（１Ｃ）、（２Ａ）等を満たす金属部材１０３の調製方法について説明する。
このような金属部材１０３は、例えば、エッチング剤を用いて粗化処理することにより形成することができる。
ここで、エッチング剤を用いて金属部材の表面を粗化処理すること自体は従来技術においても行われてきた。しかし、本実施形態では、エッチング剤の種類および濃度、粗化処理の温度および時間、エッチング処理のタイミング、等の因子を高度に制御している。上記要件（１）〜（４）、（１Ａ）〜（１Ｃ）、（２Ａ）等を満たす金属部材１０３を得るためには、これらの因子を高度に制御することが重要となる。
以下、上記要件（１）〜（４）、（１Ａ）〜（１Ｃ）、（２Ａ）等を満たす金属部材１０３を得るための金属部材表面の粗化処理方法の一例を示す。ただし、本実施形態に係る金属部材表面の粗化処理方法は、以下の例に限定されない。
Next, a method for preparing the metal member 103 that satisfies the above requirements (1) to (4), (1A) to (1C), (2A) and the like will be described.
Such a metal member 103 can be formed, for example, by roughening using an etching agent.
Here, roughening the surface of the metal member using an etchant itself has been performed in the prior art. However, in this embodiment, factors such as the type and concentration of the etching agent, the temperature and time of the roughening process, the timing of the etching process, and the like are highly controlled. In order to obtain the metal member 103 that satisfies the above requirements (1) to (4), (1A) to (1C), (2A), etc., it is important to control these factors to a high degree.
Hereinafter, an example of the roughening method of the metal member surface for obtaining the metal member 103 which satisfy | fills the said requirements (1)-(4), (1A)-(1C), (2A) etc. is shown. However, the roughening method of the metal member surface which concerns on this embodiment is not limited to the following examples.
（１）前処理工程
まず、金属部材１０３は、樹脂部材１０５との接合側の表面に酸化膜や水酸化物等からなる厚い被膜がないことが望ましい。このような厚い被膜を除去するため、次のエッチング剤で処理する工程の前に、サンドブラスト加工、ショットブラスト加工、研削加工、バレル加工等の機械研磨や、化学研磨により表面層を研磨してもよい。また、樹脂部材１０５との接合側の表面に機械油等の著しい汚染がある場合は、水酸化ナトリウム水溶液や水酸化カリウム水溶液等のアルカリ性水溶液による処理や、脱脂を行なうことが好ましい。
(1) Pretreatment process First, it is desirable that the metal member 103 does not have a thick film made of an oxide film, hydroxide, or the like on the surface on the joint side with the resin member 105. In order to remove such a thick film, the surface layer may be polished by mechanical polishing such as sand blasting, shot blasting, grinding, barrel processing, or chemical polishing before the next etching step. Good. Further, when there is significant contamination of machine oil or the like on the surface on the joint side with the resin member 105, it is preferable to perform treatment with an alkaline aqueous solution such as a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution, or degreasing.
（２）表面粗化処理工程
本実施形態において金属部材の表面粗化処理方法としては、後述する酸系エッチング剤による処理を特定のタイミングで行うことが好ましい。具体的には、該酸系エッチング剤による処理を表面粗化処理工程の最終段階で行うことが好ましい。
(2) Surface roughening treatment process In this embodiment, as a surface roughening treatment method of a metal member, it is preferable to perform the process by the acid type etching agent mentioned later at a specific timing. Specifically, the treatment with the acid-based etching agent is preferably performed at the final stage of the surface roughening treatment step.
なお、上述した特許文献５には、アルミニウムを含む金属材料からなる金属部材の表面粗化処理に用いるエッチング剤として、アルカリ系エッチング剤を用いる態様、アルカリ系エッチング剤と酸系エッチング剤を併用する態様、酸系エッチング剤で処理した後アルカリ系溶液で洗浄する態様が開示されている。
当該アルカリ系エッチング剤は、金属部材との反応が穏やかなため、作業性の観点からは好ましく用いられる。しかし、本発明者らの検討によれば、このようなアルカリ系エッチング剤は反応性が穏やかであるため、金属部材表面の粗化処理の度合いが弱く、深い凹凸形状を形成するのが困難であることが明らかになった。また、酸系エッチング剤処理を行った後アルカリ系エッチング剤やアルカリ系溶液を併用する場合には、酸系エッチング剤によって形成した深い凹凸形状を後のアルカリ系エッチング剤やアルカリ系溶液での処理により該凹凸形状を幾分か滑らかにしてしまうことが明らかになった。
In Patent Document 5 described above, as an etchant used for surface roughening treatment of a metal member made of a metal material containing aluminum, an aspect using an alkaline etchant, an alkaline etchant and an acid etchant are used in combination. An embodiment is disclosed in which an acid-based etching agent is treated and then washed with an alkaline solution.
The alkaline etching agent is preferably used from the viewpoint of workability because the reaction with the metal member is gentle. However, according to the study by the present inventors, since such an alkaline etching agent has a mild reactivity, the degree of roughening treatment on the surface of the metal member is weak and it is difficult to form a deep uneven shape. It became clear that there was. In addition, when an alkaline etchant or an alkaline solution is used in combination after an acid etchant treatment, the deep uneven shape formed by the acid etchant is treated with the subsequent alkaline etchant or alkaline solution. It became clear that the uneven shape was made somewhat smooth.
上記酸系エッチング剤を用いて粗化処理する方法としては、浸漬、スプレー等による処理方法が挙げられる。処理温度は２０〜４０℃が好ましく、処理時間は５〜３５０秒程度が好ましく、金属部材表面をより均一に粗化できる観点から、２０〜３００秒がより好ましく、５０〜３００秒が特に好ましい。 Examples of the roughening treatment using the acid-based etching agent include treatment methods such as immersion and spraying. The treatment temperature is preferably 20 to 40 ° C., the treatment time is preferably about 5 to 350 seconds, 20 to 300 seconds are more preferred, and 50 to 300 seconds are particularly preferred from the viewpoint that the surface of the metal member can be more uniformly roughened.
上記酸系エッチング剤を用いた粗化処理によって、金属部材１０３の表面が凹凸形状に粗化される。上記酸系エッチング剤を用いた際の金属部材１０３の深さ方向のエッチング量（溶解量）は、溶解した金属部材１０３の質量、比重および表面積から算出した場合、０．１〜５００μｍであることが好ましく、５〜５００μｍであることがより好ましく、５〜１００μｍであることが更に好ましい。エッチング量が上記下限値以上であれば、金属部材１０３と樹脂部材１０５との間の接合強度をより向上させることができる。また、エッチング量が上記上限値以下であれば、処理コストの低減が可能となる。エッチング量は、処理温度や処理時間等により調整できる。 By the roughening treatment using the acid-based etching agent, the surface of the metal member 103 is roughened into an uneven shape. The etching amount (dissolution amount) in the depth direction of the metal member 103 when using the acid-based etching agent is 0.1 to 500 μm when calculated from the mass, specific gravity and surface area of the dissolved metal member 103. Is more preferable, it is more preferable that it is 5-500 micrometers, and it is still more preferable that it is 5-100 micrometers. When the etching amount is equal to or greater than the lower limit, the bonding strength between the metal member 103 and the resin member 105 can be further improved. Further, if the etching amount is equal to or less than the above upper limit value, the processing cost can be reduced. The etching amount can be adjusted by the processing temperature, processing time, and the like.
なお、本実施形態では、上記酸系エッチング剤を用いて金属部材を粗化処理する際、金属部材表面の全面を粗化処理してもよく、樹脂部材１０５が接合される面だけを部分的に粗化処理してもよい。 In this embodiment, when the metal member is roughened using the acid-based etching agent, the entire surface of the metal member may be roughened, and only the surface to which the resin member 105 is bonded is partially formed. The roughening treatment may be performed.
（３）後処理工程
本実施形態では、上記表面粗化処理工程の後、通常、水洗および乾燥を行うことが好ましい。水洗の方法については特に制限はないが浸漬または流水にて所定時間洗浄することが好ましい。
(3) Post-treatment step In this embodiment, it is usually preferable to perform washing and drying after the surface roughening treatment step. Although there is no restriction | limiting in particular about the method of water washing, It is preferable to wash | clean for predetermined time with immersion or flowing water.
さらに、後処理工程としては、上記酸系エッチング剤を用いた処理により生じたスマット等を除去するため、超音波洗浄を施すことが好ましい。超音波洗浄の条件は、生じたスマット等を除去することができる条件であれば特に限定されないが、用いる溶媒としては水が好ましく、また、処理時間としては、好ましくは１〜２０分間である。 Furthermore, as a post-treatment step, it is preferable to perform ultrasonic cleaning in order to remove smut and the like generated by the treatment using the acid-based etching agent. The ultrasonic cleaning conditions are not particularly limited as long as the generated smut and the like can be removed, but the solvent used is preferably water, and the treatment time is preferably 1 to 20 minutes.
（酸系エッチング剤）
本実施形態において、金属部材表面の粗化処理に用いられるエッチング剤としては、後述する特定の酸系エッチング剤が好ましい。上記特定のエッチング剤で処理することにより、金属部材の表面に、非晶性熱可塑性樹脂（Ａ）を含む樹脂部材との間の密着性向上に適した凹凸形状が形成され、そのアンカー効果により金属部材１０３と樹脂部材１０５との間の接合強度がより一層向上するものと考えられる。
(Acid etching agent)
In this embodiment, as an etching agent used for the roughening process of the metal member surface, the specific acid type etching agent mentioned later is preferable. By treating with the above specific etching agent, a concavo-convex shape suitable for improving adhesion with the resin member containing the amorphous thermoplastic resin (A) is formed on the surface of the metal member. It is considered that the bonding strength between the metal member 103 and the resin member 105 is further improved.
以下、本実施形態で使用できる酸系エッチング剤の成分について説明する。 Hereinafter, the components of the acid-based etching agent that can be used in this embodiment will be described.
上記酸系エッチング剤は、第二鉄イオンおよび第二銅イオンの少なくとも一方と、酸と、を含み、必要に応じて、マンガンイオン、各種添加剤等を含むことができる。 The acid-based etching agent contains at least one of ferric ions and cupric ions and an acid, and may contain manganese ions, various additives, and the like as necessary.
・第二鉄イオン
上記第二鉄イオンは、金属部材を酸化する成分であり、第二鉄イオン源を配合することによって、酸系エッチング剤中に該第二鉄イオンを含有させることができる。上記第二鉄イオン源としては、硝酸第二鉄、硫酸第二鉄、塩化第二鉄等が挙げられる。上記第二鉄イオン源のうちでは、塩化第二鉄が溶解性に優れ、安価であるという点から好ましい。
-Ferric ion The said ferric ion is a component which oxidizes a metal member, and this ferric ion can be contained in an acid type etching agent by mix | blending a ferric ion source. Examples of the ferric ion source include ferric nitrate, ferric sulfate, and ferric chloride. Among the ferric ion sources, ferric chloride is preferable because it has excellent solubility and is inexpensive.
本実施形態において、酸系エッチング剤中の上記第二鉄イオンの含有量は、好ましくは０．０１〜２０質量％、より好ましくは０．１〜１２質量％、さらに好ましくは０．５〜７質量％、さらにより好ましくは１〜６質量％、特に好ましくは１〜５質量％である。上記第二鉄イオンの含有量が上記下限値以上であれば、金属部材の粗化速度（溶解速度）の低下を防ぐことができる。一方、上記第二鉄イオンの含有量が上記上限値以下であれば、粗化速度を適正に維持することができるため、金属部材１０３と樹脂部材１０５との間の接合強度向上により適した均一な粗化が可能になる。 In this embodiment, content of the said ferric ion in an acid type etching agent becomes like this. Preferably it is 0.01-20 mass%, More preferably, it is 0.1-12 mass%, More preferably, it is 0.5-7 % By mass, still more preferably 1-6% by mass, particularly preferably 1-5% by mass. If content of the said ferric ion is more than the said lower limit, the fall of the roughening rate (dissolution rate) of a metal member can be prevented. On the other hand, if the content of the ferric ion is not more than the above upper limit value, the roughening rate can be properly maintained, so that it is more suitable for improving the bonding strength between the metal member 103 and the resin member 105. Roughening becomes possible.
・第二銅イオン
上記第二銅イオンは金属部材を酸化する成分であり、第二銅イオン源を配合することによって、酸系エッチング剤中に該第二銅イオン含有させることができる。上記第二銅イオン源としては、硫酸第二銅、塩化第二銅、硝酸第二銅、水酸化第二銅等が挙げられる。上記第二銅イオン源のうちでは、硫酸第二銅、塩化第二銅が安価であるという点から好ましい。
-Cupric ion The said cupric ion is a component which oxidizes a metal member, and can mix | blend this cupric ion in an acid type etching agent by mix | blending a cupric ion source. Examples of the cupric ion source include cupric sulfate, cupric chloride, cupric nitrate, and cupric hydroxide. Of the cupric ion sources, cupric sulfate and cupric chloride are preferred because they are inexpensive.
本実施形態において、酸系エッチング剤中の上記第二銅イオンの含有量は、０．００１〜１０質量％であることが好ましく、より好ましくは０．０１〜７質量％、さらに好ましくは０．０５〜１質量％、さらにより好ましくは０．１〜０．８質量％、さらにより好ましくは０．１５〜０．７質量％、特に好ましくは０．１５〜０．４質量％である。上記第二銅イオンの含有量が上記下限値以上であれば、金属部材の粗化速度（溶解速度）の低下を防ぐことができる。一方、上記第二銅イオンの含有量が上記上限値以下であれば、粗化速度を適正に維持することができるため、金属部材１０３と樹脂部材１０５との間の接合強度向上により適した均一な粗化が可能になる。 In this embodiment, it is preferable that content of the said cupric ion in an acid type etching agent is 0.001-10 mass%, More preferably, it is 0.01-7 mass%, More preferably, it is 0.00. It is 05-1 mass%, More preferably, it is 0.1-0.8 mass%, More preferably, it is 0.15-0.7 mass%, Most preferably, it is 0.15-0.4 mass%. If content of the said cupric ion is more than the said lower limit, the fall of the roughening rate (dissolution rate) of a metal member can be prevented. On the other hand, if the content of the cupric ion is less than or equal to the above upper limit value, the roughening rate can be maintained appropriately, so that it is more suitable for improving the bonding strength between the metal member 103 and the resin member 105. Roughening becomes possible.
上記酸系エッチング剤は、第二鉄イオンおよび第二銅イオンの一方のみを含むものであってもよく、両方を含むものであってもよいが、第二鉄イオンおよび第二銅イオンの両方を含むことが好ましい。酸系エッチング剤が第二鉄イオンおよび第二銅イオンの両方を含むことで、金属部材１０３と樹脂部材１０５との間の接合強度向上により適した良好な粗化形状が容易に得られる。 The acid-based etching agent may contain only one of ferric ion and cupric ion, or may contain both, but both ferric ion and cupric ion It is preferable to contain. When the acid-based etching agent contains both ferric ions and cupric ions, a good roughened shape that is more suitable for improving the bonding strength between the metal member 103 and the resin member 105 can be easily obtained.
上記酸系エッチング剤が、第二鉄イオンおよび第二銅イオンの両方を含む場合、第二鉄イオンおよび第二銅イオンのそれぞれの含有量が、上記範囲であることが好ましい。また、酸系エッチング剤中の第二鉄イオンと第二銅イオンの含有量の合計は、０．０１１〜２０質量％であることが好ましく、より好ましくは０．１〜１５質量％、さらに好ましくは０．５〜１０質量％、特に好ましくは１〜５質量％である。 When the acid-based etching agent contains both ferric ions and cupric ions, the contents of ferric ions and cupric ions are preferably in the above ranges. The total content of ferric ions and cupric ions in the acid-based etching agent is preferably 0.011 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably. Is 0.5 to 10% by mass, particularly preferably 1 to 5% by mass.
・マンガンイオン
上記酸系エッチング剤には、金属部材表面をむらなく一様に粗化するために、マンガンイオンが含まれていてもよい。マンガンイオンは、マンガンイオン源を配合することによって、酸系エッチング剤中に該マンガンイオンを含有させることができる。上記マンガンイオン源としては、硫酸マンガン、塩化マンガン、酢酸マンガン、フッ化マンガン、硝酸マンガン等が挙げられる。上記マンガンイオン源のうちでは、硫酸マンガン、塩化マンガンが安価である等の点から好ましい。
Manganese ions The acid-based etching agent may contain manganese ions in order to uniformly roughen the surface of the metal member. Manganese ions can be contained in the acid-based etching agent by blending a manganese ion source. Examples of the manganese ion source include manganese sulfate, manganese chloride, manganese acetate, manganese fluoride, and manganese nitrate. Among the above manganese ion sources, manganese sulfate and manganese chloride are preferable from the viewpoint of being inexpensive.
本実施形態において、酸系エッチング剤中の上記マンガンイオンの含有量は、０〜１質量％であることが好ましく、より好ましくは０〜０．５質量％である。 In this embodiment, it is preferable that content of the said manganese ion in an acid type etching agent is 0-1 mass%, More preferably, it is 0-0.5 mass%.
・酸
上記酸は、第二鉄イオンおよび／または第二銅イオンにより酸化された金属を溶解させる成分である。上記酸としては、塩酸、臭化水素酸、硫酸、硝酸、リン酸、過塩素酸、スルファミン酸等の無機酸や、スルホン酸、カルボン酸等の有機酸が挙げられる。上記カルボン酸としては、ギ酸、酢酸、クエン酸、シュウ酸、リンゴ酸等が挙げられる。上記酸系エッチング剤には、これらの酸を一種または二種以上配合することができる。上記無機酸のうちでは、臭気がほとんどなく、安価である点から硫酸が好ましい。また、上記有機酸のうちでは、粗化形状の均一性の観点から、カルボン酸が好ましい。
-Acid The acid is a component that dissolves a metal oxidized by ferric ions and / or cupric ions. Examples of the acid include inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, and sulfamic acid, and organic acids such as sulfonic acid and carboxylic acid. Examples of the carboxylic acid include formic acid, acetic acid, citric acid, oxalic acid, malic acid and the like. One or more of these acids can be added to the acid-based etching agent. Of the inorganic acids, sulfuric acid is preferred because it has almost no odor and is inexpensive. Among the organic acids, carboxylic acid is preferable from the viewpoint of uniformity of the roughened shape.
本実施形態において、酸系エッチング剤中の上記酸の含有量は、０．１〜５０質量％であることが好ましく、０．５〜５０質量％であることがより好ましく、１〜５０質量％であることがさらに好ましく、１〜３０質量％であることがさらにより好ましく、１〜２５質量％であることがさらにより好ましく、２〜１８質量％であることがさらにより好ましい。上記酸の含有量が上記下限値以上であれば、金属の粗化速度（溶解速度）の低下を防止できる。一方、上記酸の含有量が上記上限値以下であれば、液温が低下した際の金属塩の結晶析出を防止できるため、作業性を向上できる。 In the present embodiment, the acid content in the acid-based etching agent is preferably 0.1 to 50% by mass, more preferably 0.5 to 50% by mass, and 1 to 50% by mass. It is still more preferable, it is still more preferable that it is 1-30 mass%, it is still more preferable that it is 1-25 mass%, and it is still more preferable that it is 2-18 mass%. If content of the said acid is more than the said lower limit, the fall of the metal roughening rate (dissolution rate) can be prevented. On the other hand, if the content of the acid is not more than the upper limit, it is possible to prevent crystal precipitation of the metal salt when the liquid temperature is lowered, so that workability can be improved.
・他の成分
本実施形態において使用できる酸系エッチング剤には、指紋等の表面汚染物による粗化のむらを防ぐために界面活性剤を添加してもよく、必要に応じて他の添加剤を添加してもよい。他の添加剤としては、深い凹凸を形成するために添加されるハロゲン化物イオン源、例えば、塩化ナトリウム、塩化カリウム、臭化ナトリウム、臭化カリウム等を例示できる。あるいは、粗化処理速度を上げるために添加されるチオ硫酸イオン、チオ尿素等のチオ化合物や、より均一な粗化形状を得るために添加されるイミダゾール、トリアゾール、テトラゾール等のアゾール類や、粗化反応を制御するために添加されるｐＨ調整剤等も例示できる。これら他の成分を添加する場合、その合計含有量は、酸系エッチング剤中に０．０１〜１０質量％程度であることが好ましい。
Other components To the acid-based etching agent that can be used in the present embodiment, a surfactant may be added to prevent unevenness due to surface contaminants such as fingerprints, and other additives may be added as necessary. May be. Other additives include halide ion sources added to form deep irregularities, such as sodium chloride, potassium chloride, sodium bromide, potassium bromide and the like. Alternatively, thio compounds such as thiosulfate ions and thiourea added to increase the roughening treatment speed, azoles such as imidazole, triazole and tetrazole added to obtain a more uniform roughened shape, Examples thereof include a pH adjuster added to control the oxidization reaction. When these other components are added, the total content is preferably about 0.01 to 10% by mass in the acid-based etching agent.
本実施形態の酸系エッチング剤は、上記の各成分をイオン交換水等に溶解させることにより容易に調製することができる。 The acid-based etching agent of this embodiment can be easily prepared by dissolving each of the above components in ion-exchanged water or the like.
＜樹脂部材＞
以下、本実施形態に係る樹脂部材１０５について説明する。
樹脂部材１０５は非晶性熱可塑性樹脂（Ａ）を含む樹脂組成物（Ｐ）からなる。樹脂組成物（Ｐ）は、樹脂成分として非晶性熱可塑性樹脂（Ａ）と、必要に応じて充填材（Ｂ）と、含む。さらに、樹脂組成物（Ｐ）は必要に応じてその他の配合剤を含む。なお、便宜上、樹脂部材１０５が非晶性熱可塑性樹脂（Ａ）のみからなる場合であっても、樹脂部材１０５は樹脂組成物（Ｐ）からなると記載する。
<Resin member>
Hereinafter, the resin member 105 according to the present embodiment will be described.
The resin member 105 is made of a resin composition (P) containing an amorphous thermoplastic resin (A). The resin composition (P) contains an amorphous thermoplastic resin (A) as a resin component and a filler (B) as necessary. Furthermore, the resin composition (P) contains other compounding agents as necessary. For convenience, it is described that the resin member 105 is made of the resin composition (P) even when the resin member 105 is made of only the amorphous thermoplastic resin (A).
（非晶性熱可塑性樹脂（Ａ））
本実施形態において、非晶性熱可塑性樹脂（Ａ）とは、示差走査熱量測定（ＤＳＣ）を用いた熱分析測定において、結晶の融解による明確な吸熱ピークはなく、常温において固体で、ガラス転移温度以上の温度において熱可塑化するものを指す。
(Amorphous thermoplastic resin (A))
In the present embodiment, the amorphous thermoplastic resin (A) is a thermal analysis measurement using differential scanning calorimetry (DSC), which has no clear endothermic peak due to crystal melting, is solid at room temperature, and has a glass transition It refers to those that are thermoplasticized at temperatures above that.
非晶性熱可塑性樹脂（Ａ）としては特に限定されないが、例えば、ポリオレフィン系樹脂、ポリメタクリル酸メチル樹脂等のポリメタクリル系樹脂、ポリアクリル酸メチル樹脂等のポリアクリル系樹脂、ポリスチレン樹脂、ポリビニルアルコール−ポリ塩化ビニル共重合体樹脂、ポリビニルアセタール樹脂、ポリビニルブチラール樹脂、ポリビニルホルマール樹脂、ポリメチルペンテン樹脂、無水マレイン酸−スチレン共重合体樹脂、ポリカーボネート樹脂、ポリフェニレンエーテル樹脂、ポリエーテルエーテルケトン樹脂、ポリエーテルケトン樹脂等の芳香族ポリエーテルケトン、ポリエステル系樹脂、ポリアミド系樹脂、ポリアミドイミド樹脂、ポリイミド樹脂、ポリエーテルイミド樹脂、スチレン系エラストマー、ポリオレフィン系エラストマー、ポリウレタン系エラストマー、ポリエステル系エラストマー、ポリアミド系エラストマー、アイオノマー、アミノポリアクリルアミド樹脂、イソブチレン無水マレイン酸コポリマー、ＡＢＳ、ＡＣＳ、ＡＥＳ、ＡＳ、ＡＳＡ、ＭＢＳ、エチレン−塩化ビニルコポリマー、エチレン−酢酸ビニルコポリマー、エチレン−酢酸ビニル−塩化ビニルグラフトポリマー、エチレン−ビニルアルコールコポリマー、塩素化ポリ塩化ビニル樹脂、塩素化ポリエチレン樹脂、塩素化ポリプロピレン樹脂、カルボキシビニルポリマー、ケトン樹脂、非晶性コポリエステル樹脂、ノルボルネン樹脂、フッ素プラスチック、ポリテトラフルオロエチレン樹脂、フッ素化エチレンポリプロピレン樹脂、ＰＦＡ、ポリクロロフルオロエチレン樹脂、エチレンテトラフルオロエチレンコポリマー、ポリフッ化ビニリデン樹脂、ポリフッ化ビニル樹脂、ポリアリレート樹脂、熱可塑性ポリイミド樹脂、ポリ塩化ビニリデン樹脂、ポリ塩化ビニル樹脂、ポリ酢酸ビニル樹脂、ポリサルホン樹脂、ポリパラメチルスチレン樹脂、ポリアリルアミン樹脂、ポリビニルエーテル樹脂、ポリフェニレンオキシド樹脂、ポリフェニレンスルフィド（ＰＰＳ）樹脂、ポリメチルペンテン樹脂、オリゴエステルアクリレート、キシレン樹脂、マレイン酸樹脂、ポリヒドロキシブチレート樹脂、ポリスルホン樹脂、ポリ乳酸樹脂、ポリグルタミン酸樹脂、ポリカプロラクトン樹脂、ポリエーテルスルホン樹脂、ポリフェニルスルホン樹脂、ポリスルホン樹脂、ポリアクリロニトリル樹脂、スチレン−アクリロニトリル共重合体樹脂等が挙げられる。これらの非晶性熱可塑性樹脂（Ａ）は一種単独で使用してもよいし、二種以上組み合わせて使用してもよい。 The amorphous thermoplastic resin (A) is not particularly limited. For example, a polyolefin resin, a polymethacrylic resin such as a polymethyl methacrylate resin, a polyacrylic resin such as a polymethyl acrylate resin, a polystyrene resin, and a polyvinyl resin. Alcohol-polyvinyl chloride copolymer resin, polyvinyl acetal resin, polyvinyl butyral resin, polyvinyl formal resin, polymethylpentene resin, maleic anhydride-styrene copolymer resin, polycarbonate resin, polyphenylene ether resin, polyether ether ketone resin, Aromatic polyether ketones such as polyether ketone resins, polyester resins, polyamide resins, polyamide imide resins, polyimide resins, polyether imide resins, styrene elastomers, polyolefin resins Stomer, polyurethane elastomer, polyester elastomer, polyamide elastomer, ionomer, aminopolyacrylamide resin, isobutylene maleic anhydride copolymer, ABS, ACS, AES, AS, ASA, MBS, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer , Ethylene-vinyl acetate-vinyl chloride graft polymer, ethylene-vinyl alcohol copolymer, chlorinated polyvinyl chloride resin, chlorinated polyethylene resin, chlorinated polypropylene resin, carboxyvinyl polymer, ketone resin, amorphous copolyester resin, norbornene resin , Fluoroplastic, Polytetrafluoroethylene resin, Fluorinated ethylene polypropylene resin, PFA, Polychlorofluoroethylene resin, Ethylene Tetrafluoroethylene copolymer, polyvinylidene fluoride resin, polyvinyl fluoride resin, polyarylate resin, thermoplastic polyimide resin, polyvinylidene chloride resin, polyvinyl chloride resin, polyvinyl acetate resin, polysulfone resin, polyparamethylstyrene resin, polyallylamine Resin, polyvinyl ether resin, polyphenylene oxide resin, polyphenylene sulfide (PPS) resin, polymethylpentene resin, oligoester acrylate, xylene resin, maleic acid resin, polyhydroxybutyrate resin, polysulfone resin, polylactic acid resin, polyglutamic acid resin, Polycaprolactone resin, polyethersulfone resin, polyphenylsulfone resin, polysulfone resin, polyacrylonitrile resin, styrene-acrylonitrile copolymer Examples include coalesced resins. These amorphous thermoplastic resins (A) may be used alone or in combination of two or more.
これらの中でも、上記非晶性熱可塑性樹脂（Ａ）としては、ポリスチレン樹脂、ポリアクリロニトリル樹脂、スチレン−アクリロニトリル共重合体樹脂、アクリロニトリル−ブタジエン−スチレン共重合体樹脂（ＡＢＳ樹脂）、ポリメタクリル酸メチル樹脂（ＰＭＭＡ樹脂）、およびポリカーボネート樹脂（ＰＣ樹脂）から選択される一種または二種以上が好ましい。 Among these, the amorphous thermoplastic resin (A) includes polystyrene resin, polyacrylonitrile resin, styrene-acrylonitrile copolymer resin, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), polymethyl methacrylate. One or more selected from resins (PMMA resins) and polycarbonate resins (PC resins) are preferred.
（充填材（Ｂ））
樹脂組成物（Ｐ）は、金属部材１０３と樹脂部材１０５との線膨張係数差の調整や樹脂部材１０５の機械的強度を向上させる観点から、充填材（Ｂ）をさらに含んでもよい。
(Filler (B))
The resin composition (P) may further include a filler (B) from the viewpoint of adjusting the difference in coefficient of linear expansion between the metal member 103 and the resin member 105 and improving the mechanical strength of the resin member 105.
充填材（Ｂ）としては、例えば、ガラス繊維、炭素繊維、炭素粒子、粘土、タルク、シリカ、ミネラル、セルロース繊維からなる群から一種または二種以上を選ぶことができる。これらのうち、好ましくは、ガラス繊維、炭素繊維、タルク、ミネラルから選択される一種または二種以上である。 As a filler (B), 1 type, or 2 or more types can be selected from the group which consists of glass fiber, carbon fiber, carbon particle, clay, talc, silica, a mineral, and a cellulose fiber, for example. Among these, Preferably, they are 1 type, or 2 or more types selected from glass fiber, carbon fiber, talc, and a mineral.
充填材（Ｂ）の形状は特に限定されず、繊維状、粒子状、板状等どのような形状であってもよい。 The shape of the filler (B) is not particularly limited, and may be any shape such as a fiber shape, a particle shape, or a plate shape.
なお、樹脂組成物（Ｐ）が充填材（Ｂ）を含む場合、その含有量は、非晶性熱可塑性樹脂（Ａ）１００質量部に対して、好ましくは１質量部以上１００質量部以下であり、より好ましくは５質量部以上９０質量部以下であり、特に好ましくは１０質量部以上８０質量部以下である。 In addition, when the resin composition (P) includes the filler (B), the content thereof is preferably 1 part by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the amorphous thermoplastic resin (A). Yes, more preferably 5 parts by mass or more and 90 parts by mass or less, and particularly preferably 10 parts by mass or more and 80 parts by mass or less.
充填材（Ｂ）は、樹脂部材１０５の剛性を高める効果の他、樹脂部材１０５の線膨張係数を制御できる効果がある。特に、本実施形態の金属部材１０３と樹脂部材１０５との複合体の場合は、金属部材１０３と樹脂部材１０５との形状安定性の温度依存性が大きく異なることが多いので、大きな温度変化が起こると複合体に歪みが掛かりやすい。樹脂部材１０５が上記充填材（Ｂ）を含有することにより、この歪みを低減することができる。また、上記充填材（Ｂ）の含有量が上記範囲内であることにより、靱性の低減を抑制することができる。 The filler (B) has an effect of controlling the linear expansion coefficient of the resin member 105 in addition to the effect of increasing the rigidity of the resin member 105. In particular, in the case of the composite of the metal member 103 and the resin member 105 according to the present embodiment, the temperature dependence of the shape stability of the metal member 103 and the resin member 105 is often greatly different, so that a large temperature change occurs. And the composite is easily distorted. This distortion can be reduced when the resin member 105 contains the filler (B). Moreover, when content of the said filler (B) exists in the said range, reduction of toughness can be suppressed.
（その他の配合剤）
樹脂組成物（Ｐ）には、個々の機能を付与する目的でその他の配合剤を含んでもよい。
上記配合剤としては、熱安定剤、酸化防止剤、顔料、耐候剤、難燃剤、可塑剤、分散剤、滑剤、離型剤、帯電防止剤等、耐衝撃性改質剤が挙げられる。
(Other ingredients)
The resin composition (P) may contain other compounding agents for the purpose of imparting individual functions.
Examples of the compounding agents include thermal stabilizers, antioxidants, pigments, weathering agents, flame retardants, plasticizers, dispersants, lubricants, mold release agents, antistatic agents, and other impact resistance modifiers.
（樹脂組成物（Ｐ）の製造方法）
樹脂組成物（Ｐ）の製造方法は特に限定されず、一般的に公知の方法により製造することができる。例えば、以下の方法が挙げられる。まず、非晶性熱可塑性樹脂（Ａ）、必要に応じて充填材（Ｂ）、さらに必要に応じて上記その他の配合剤とを、バンバリーミキサー、単軸押出機、２軸押出機、高速２軸押出機等の混合装置を用いて、混合または溶融混合することにより、樹脂組成物（Ｐ）が得られる。
(Production method of resin composition (P))
The manufacturing method of resin composition (P) is not specifically limited, Generally, it can manufacture by a well-known method. For example, the following method is mentioned. First, an amorphous thermoplastic resin (A), a filler (B) as necessary, and the above other compounding agents as needed, a Banbury mixer, a single screw extruder, a twin screw extruder, a high speed 2 The resin composition (P) is obtained by mixing or melt-mixing using a mixing apparatus such as a screw extruder.
［金属／樹脂複合構造体の製造方法］
つづいて、本実施形態に係る金属／樹脂複合構造体１０６の製造方法について説明する。
金属／樹脂複合構造体１０６の製造方法は、以下の（ｉ）〜（ｉｉ）の工程を含む。
（ｉ）金型のキャビティ部に、間隔周期が５ｎｍ以上５００μｍ以下である凸部が林立した微細凹凸表面を有する金属部材１０３を配置する工程
（ｉｉ）上記キャビティ部に樹脂組成物（Ｐ）を射出することにより金属部材１０３と樹脂部材１０５とを接合する工程
以下、具体的に説明する。
[Method for producing metal / resin composite structure]
Next, a method for manufacturing the metal / resin composite structure 106 according to this embodiment will be described.
The manufacturing method of the metal / resin composite structure 106 includes the following steps (i) to (ii).
(I) A step of placing the metal member 103 having a fine uneven surface with a convex portion having an interval interval of 5 nm or more and 500 μm or less in the cavity portion of the mold (ii) The resin composition (P) is placed in the cavity portion The step of joining the metal member 103 and the resin member 105 by injection will be specifically described below.
まず、（ｉ）金型を用意し、その金型を開いてそのキャビティ部（空間部）に金属部材１０３を配置する。（ｉｉ）その後、金型を閉じ、樹脂組成物（Ｐ）の少なくとも一部が金属部材１０３の上記微細凹凸表面と接するように、上記金型の上記キャビティ部に樹脂組成物（Ｐ）を射出して固化し、金属部材１０３と樹脂部材１０５とを接合する。その後、金型を開き離型することにより、金属／樹脂複合構造体１０６を得ることができる。上記金型としては、例えば、高速ヒートサイクル成形（ＲＨＣＭ、ヒート＆クール成形）で一般的に使用される射出成形用金型を用いることができる。 First, (i) a mold is prepared, the mold is opened, and the metal member 103 is placed in the cavity (space). (Ii) Thereafter, the mold is closed, and the resin composition (P) is injected into the cavity portion of the mold so that at least a part of the resin composition (P) is in contact with the fine uneven surface of the metal member 103. Then, the metal member 103 and the resin member 105 are joined. Thereafter, the metal / resin composite structure 106 can be obtained by opening the mold and releasing the mold. As the mold, for example, an injection mold generally used in high-speed heat cycle molding (RHCM, heat & cool molding) can be used.
ここで、上記（ｉｉ）の工程において、樹脂組成物（Ｐ）の射出開始から保圧完了までの間、上記金型の表面温度を非晶性熱可塑性樹脂（Ａ）のガラス転移温度（以下、Ｔｇとも呼ぶ。）以上、好ましくはＴｇ＋（５以上１００以下）℃以上の温度に維持する。
これにより、非晶性熱可塑性樹脂（Ａ）を溶融させた状態に保ちながら、金属部材１０３の上記微細凹凸表面に非晶性熱可塑性樹脂（Ａ）を高圧でより長い時間接触させることができる。
その結果、金属部材１０３の微細凹凸形状の凹部の奥まで非晶性熱可塑性樹脂（Ａ）を十分に侵入させることができるため、金属部材１０３と樹脂部材１０５との間に物理的な抵抗力（アンカー効果）が効果的に発現し、接合強度に優れた金属／樹脂複合構造体１０６を安定的に得ることができる。
Here, in the step (ii), the surface temperature of the mold is set to the glass transition temperature of the amorphous thermoplastic resin (A) (below) from the start of injection of the resin composition (P) to the completion of pressure holding. , Also referred to as Tg.), Preferably at a temperature of Tg + (5 or more and 100 or less) ° C. or more.
Thereby, the amorphous thermoplastic resin (A) can be brought into contact with the fine uneven surface of the metal member 103 at a high pressure for a longer time while keeping the amorphous thermoplastic resin (A) in a molten state. .
As a result, the amorphous thermoplastic resin (A) can be sufficiently penetrated to the depth of the concave portion of the fine uneven shape of the metal member 103, so that the physical resistance force between the metal member 103 and the resin member 105 can be reduced. The (anchor effect) is effectively expressed, and the metal / resin composite structure 106 having excellent bonding strength can be stably obtained.
また、上記（ｉｉ）の工程において、上記保圧完了後、上記金型の表面温度を非晶性熱可塑性樹脂（Ａ）のガラス転移温度未満、好ましくはＴｇ−（５以上１００以下）℃以下の温度に冷却する。
これにより、溶融状態の非晶性熱可塑性樹脂（Ａ）を急速に固化させることができる。その結果、金属／樹脂複合構造体１０６の成形サイクルを短縮できるため、金属／樹脂複合構造体１０６を効率よく得ることができる。
In the step (ii), after completion of the pressure holding, the surface temperature of the mold is lower than the glass transition temperature of the amorphous thermoplastic resin (A), preferably Tg− (5 to 100) ° C. Cool to the temperature of.
Thereby, the amorphous thermoplastic resin (A) in a molten state can be rapidly solidified. As a result, since the molding cycle of the metal / resin composite structure 106 can be shortened, the metal / resin composite structure 106 can be obtained efficiently.
以上から、本実施形態に係る金属／樹脂複合構造体１０６の製造方法によれば、金属部材１０３と樹脂部材１０５との接合強度に優れた金属／樹脂複合構造体１０６を安定的に、かつ、効率よく製造することができる。 As described above, according to the manufacturing method of the metal / resin composite structure 106 according to the present embodiment, the metal / resin composite structure 106 having excellent bonding strength between the metal member 103 and the resin member 105 can be stably obtained. It can be manufactured efficiently.
上記金型の表面温度の調整は、急速加熱冷却装置を金型に接続することにより、実施することができる。急速加熱冷却装置は、一般的に使用されている方式を採用することができる。 The surface temperature of the mold can be adjusted by connecting a rapid heating / cooling device to the mold. As the rapid heating / cooling device, a generally used method can be adopted.
加熱方法として、蒸気式、加圧熱水式、熱水式、熱油式、電気ヒータ式、電磁誘導過熱式のいずれか１方式またはそれらを複数組み合わせた方式でよい。
具体的には、金型の表面の近くに設けられた流路に水蒸気、温水および温油から選択される加熱媒体を導入する、あるいは電磁誘導加熱を用いることにより、上記金型の上記表面温度を非晶性熱可塑性樹脂（Ａ）のガラス転移温度以上の温度に維持することが好ましい。
As a heating method, any one of a steam type, a pressurized hot water type, a hot water type, a hot oil type, an electric heater type, an electromagnetic induction overheating type, or a combination of them may be used.
Specifically, the surface temperature of the mold is introduced by introducing a heating medium selected from water vapor, hot water and hot oil into a flow path provided near the surface of the mold, or using electromagnetic induction heating. Is preferably maintained at a temperature equal to or higher than the glass transition temperature of the amorphous thermoplastic resin (A).
冷却方法としては、冷水式、冷油式のいずれか１方式またはそれらを組み合わせた方式でよい。
具体的には、金型の表面の近くに設けられた流路に冷水および冷油から選択される冷却媒体を導入することにより、金型の表面温度を非晶性熱可塑性樹脂（Ａ）のガラス転移温度未満の温度に冷却することが好ましい。
As a cooling method, any one of a cold water type and a cold oil type or a combination thereof may be used.
Specifically, by introducing a cooling medium selected from cold water and cold oil into a flow path provided near the surface of the mold, the surface temperature of the mold is changed to that of the amorphous thermoplastic resin (A). It is preferable to cool to a temperature below the glass transition temperature.
上記（ｉｉ）の工程において、上記射出開始から上記保圧完了までの時間は、好ましくは１秒以上４０秒以下であり、より好ましくは１０秒以上３０秒以下である。
上記時間が上記下限値以上であると非晶性熱可塑性樹脂（Ａ）を溶融させた状態に保ちながら、金属部材１０３の上記微細凹凸表面に非晶性熱可塑性樹脂（Ａ）を高圧でより長い時間接触させることができる。これにより、接合強度により一層優れた金属／樹脂複合構造体１０６をより安定的に得ることができる。
また、上記時間が上記上限値以下であると、金属／樹脂複合構造体１０６の成形サイクルを短縮できるため、金属／樹脂複合構造体１０６をより効率よく得ることができる。
In the step (ii), the time from the start of injection to the completion of the pressure holding is preferably 1 second to 40 seconds, more preferably 10 seconds to 30 seconds.
The amorphous thermoplastic resin (A) is applied to the surface of the fine irregularities of the metal member 103 at a high pressure while keeping the amorphous thermoplastic resin (A) in a molten state when the time is equal to or more than the lower limit. Can be contacted for a long time. Thereby, the metal / resin composite structure 106 which is further superior in bonding strength can be obtained more stably.
Moreover, since the molding cycle of the metal / resin composite structure 106 can be shortened when the time is equal to or less than the upper limit, the metal / resin composite structure 106 can be obtained more efficiently.
また、本実施形態に係る金属／樹脂複合構造体１０６の製造方法が適用される成形方法としては、射出成形法、トランスファー成形法、圧縮成形法、反応射出成形法、ブロー成形法、熱成形法、プレス成形法などが挙げられる。これらの中でも射出成形法が好ましい。 Further, as a molding method to which the manufacturing method of the metal / resin composite structure 106 according to the present embodiment is applied, an injection molding method, a transfer molding method, a compression molding method, a reaction injection molding method, a blow molding method, and a thermoforming method are used. And a press molding method. Among these, the injection molding method is preferable.
［金属／樹脂複合構造体の用途］
本実施形態に係る金属／樹脂複合構造体１０６は、生産性が高く、形状制御の自由度も高いので、様々な用途に展開することが可能である。
さらに、本実施形態に係る金属／樹脂複合構造体１０６は、高い気密性、水密性が発現するので、これらの特性に応じた用途に好適に用いられる。
[Use of metal / resin composite structure]
Since the metal / resin composite structure 106 according to the present embodiment has high productivity and high degree of freedom in shape control, it can be developed for various applications.
Furthermore, since the metal / resin composite structure 106 according to the present embodiment exhibits high airtightness and watertightness, it is preferably used for applications according to these characteristics.
例えば、車両用構造部品、車両搭載用品、電子機器の筐体、家電機器の筐体、構造用部品、機械部品、種々の自動車用部品、電子機器用部品、家具、台所用品等の家財向け用途、医療機器、建築資材の部品、その他の構造用部品や外装用部品等が挙げられる。 For example, use for household goods such as structural parts for vehicles, on-vehicle equipment, housing for electronic equipment, housing for home appliances, structural parts, mechanical parts, various automotive parts, electronic equipment parts, furniture, kitchenware, etc. , Medical equipment, building material parts, other structural parts and exterior parts.
より具体的には、樹脂だけでは強度が足りない部分を金属がサポートする様にデザインされた次のような部品である。車両関係では、インスツルメントパネル、コンソールボックス、ドアノブ、ドアトリム、シフトレバー、ペダル類、グローブボックス、バンパー、ボンネット、フェンダー、トランク、ドア、ルーフ、ピラー、座席シート、ラジエータ、オイルパン、ステアリングホイール、ＥＣＵボックス、電装部品等が挙げられる。また、建材や家具類として、ガラス窓枠、手すり、カーテンレール、たんす、引き出し、クローゼット、書棚、机、椅子等が挙げられる。また、精密電子部品類として、コネクタ、リレー、ギヤ等が挙げられる。また、輸送容器として、輸送コンテナ、スーツケース、トランク等が挙げられる。 More specifically, the following parts are designed so that the metal supports a portion where the strength is insufficient with the resin alone. For vehicles, instrument panels, console boxes, door knobs, door trims, shift levers, pedals, glove boxes, bumpers, bonnets, fenders, trunks, doors, roofs, pillars, seats, radiators, oil pans, steering wheels, An ECU box, electrical parts, etc. Examples of building materials and furniture include glass window frames, handrails, curtain rails, chests, drawers, closets, bookcases, desks, chairs, and the like. Examples of precision electronic components include connectors, relays, and gears. Moreover, a transport container, a suitcase, a trunk, etc. are mentioned as a transport container.
また、金属部材１０３の高い熱伝導率と、非晶性熱可塑性樹脂（Ａ）の断熱的性質とを組み合わせ、ヒートマネージメントを最適に設計する機器に使用される部品用途、例えば、各種家電にも用いることができる。具体的には、冷蔵庫、洗濯機、掃除機、電子レンジ、エアコン、照明機器、電気湯沸かし器、テレビ、時計、換気扇、プロジェクター、スピーカー等の家電製品類、パソコン、携帯電話、スマートフォン、デジタルカメラ、タブレット型ＰＣ、携帯音楽プレーヤー、携帯ゲーム機、充電器、電池等電子情報機器等が挙げられる。 In addition, it combines the high thermal conductivity of the metal member 103 with the adiabatic property of the amorphous thermoplastic resin (A), and is used for parts used in equipment that optimally designs heat management, such as various home appliances. Can be used. Specifically, household appliances such as refrigerators, washing machines, vacuum cleaners, microwave ovens, air conditioners, lighting equipment, electric water heaters, televisions, clocks, ventilation fans, projectors, speakers, personal computers, mobile phones, smartphones, digital cameras, tablets Electronic information devices such as type PCs, portable music players, portable game machines, chargers, and batteries.
これらについては、金属部材１０３の表面を粗化することによって表面積が増加するため、金属部材１０３と樹脂部材１０５との間の接触面積が増加し、接触界面の熱抵抗を低減させることができることに由来する。 About these, since the surface area increases by roughening the surface of the metal member 103, the contact area between the metal member 103 and the resin member 105 increases, and the thermal resistance of the contact interface can be reduced. Derived from.
その他の用途として、玩具、スポーツ用具、靴、サンダル、鞄、フォークやナイフ、スプーン、皿等の食器類、ボールペンやシャープペン、ファイル、バインダー等の文具類、フライパンや鍋、やかん、フライ返し、おたま、穴杓子、泡だて器、トング等の調理器具、リチウムイオン２次電池用部品、ロボット等が挙げられる。 Other applications include toys, sports equipment, shoes, sandals, bags, forks and knives, spoons, dishes such as dishes, ballpoint pens and mechanical pencils, files, binders and other stationery, frying pans and pans, kettles, frying, Examples include a ladle, a hole insulator, a whisk, a cooking tool such as a tongue, a lithium ion secondary battery component, a robot, and the like.
以上、本発明の金属／樹脂複合構造体１０６の用途について述べたが、これらは本発明の用途の例示であり、上記以外の様々な用途に用いることもできる。 As mentioned above, although the use of the metal / resin composite structure 106 of this invention was described, these are illustrations of the use of this invention, and it can also be used for various uses other than the above.
以上、本発明の実施形態について述べたが、これらは本発明の例示であり、上記以外の様々な構成を採用することもできる。 As mentioned above, although embodiment of this invention was described, these are illustrations of this invention and various structures other than the above are also employable.
以下、本実施形態を、実施例・比較例を参照して詳細に説明する。なお、本実施形態は、これらの実施例の記載に何ら限定されるものではない。 Hereinafter, the present embodiment will be described in detail with reference to examples and comparative examples. In addition, this embodiment is not limited to description of these Examples at all.
なお、図１、２は各実施例の共通の図として使用する。
図１は、金属部材１０３と樹脂部材１０５との金属／樹脂複合構造体１０６の構造の一例を模式的に示した外観図である。
図２は、金属部材１０３と樹脂部材１０５との金属／樹脂複合構造体１０６を製造する過程の一例を模式的に示した構成図である。具体的には所定形状に加工され、表面に微細凹凸面を有する接合部表面１０４が形成された金属部材１０３を金型１０２内に設置し、射出成形機１０１により、樹脂組成物（Ｐ）をゲート／ランナー１０７を通して射出し、微細凹凸表面を有する金属部材１０３と一体化された金属／樹脂複合構造体１０６を製造する過程を模式的に示している。
Note that FIGS. 1 and 2 are used as a common view of each embodiment.
FIG. 1 is an external view schematically showing an example of the structure of a metal / resin composite structure 106 of a metal member 103 and a resin member 105.
FIG. 2 is a configuration diagram schematically showing an example of a process of manufacturing the metal / resin composite structure 106 of the metal member 103 and the resin member 105. Specifically, a metal member 103 that has been processed into a predetermined shape and has a joining surface 104 having a fine irregular surface on the surface is placed in a mold 102, and the resin composition (P) is injected by an injection molding machine 101. A process of manufacturing a metal / resin composite structure 106 that is injected through a gate / runner 107 and integrated with a metal member 103 having a fine uneven surface is schematically shown.
（金属部材表面の、粗さ曲線の負荷長さ率（Ｒｍｒ）、十点平均粗さ（Ｒｚ）および粗さ曲線要素の平均長さ（ＲＳｍ）の測定）
表面粗さ測定装置「サーフコム１４００Ｄ（東京精密社製）」を使用し、ＪＩＳ Ｂ０６０１（対応ＩＳＯ ４２８７）に準拠して測定される表面粗さのうち、粗さ曲線の負荷長さ率（Ｒｍｒ）、十点平均粗さ（Ｒｚ）および粗さ曲線要素の平均長さ（ＲＳｍ）を測定した。なお、測定条件は以下のとおりである。
・触針先端半径：５μｍ
・基準長さ：０．８ｍｍ
・評価長さ：４ｍｍ
・測定速度：０．０６ｍｍ／ｓｅｃ
測定は、金属部材の表面上の、平行関係にある任意の３直線部、および当該直線部と直交する任意の３直線部からなる合計６直線部についておこなった（図４参照）。なお、本実施例・比較例では、金属部材１０３の全面について粗化処理をおこなっているため、金属／樹脂複合構造体１０６の接合部表面１０４について粗さ曲線の負荷長さ率（Ｒｍｒ）、十点平均粗さ（Ｒｚ）および粗さ曲線要素の平均長さ（ＲＳｍ）の測定をおこなっても、図４に示す測定箇所と同様の評価結果が得られることが理解される。
(Measurement of load length ratio (Rmr), ten-point average roughness (Rz), and average length (RSm) of roughness curve elements on the surface of a metal member)
Of the surface roughness measured according to JIS B0601 (corresponding ISO 4287) using a surface roughness measuring device “Surfcom 1400D (manufactured by Tokyo Seimitsu Co., Ltd.)”, the load length ratio (Rmr) of the roughness curve The ten-point average roughness (Rz) and the average length (RSm) of the roughness curve elements were measured. The measurement conditions are as follows.
・ Tip tip radius: 5μm
・ Standard length: 0.8mm
・ Evaluation length: 4mm
・ Measurement speed: 0.06mm / sec
The measurement was performed on a total of six straight line portions including arbitrary three straight line portions in parallel relation on the surface of the metal member and arbitrary three straight line portions orthogonal to the straight line portion (see FIG. 4). In this example / comparative example, since the entire surface of the metal member 103 is roughened, the load length ratio (Rmr) of the roughness curve for the joint surface 104 of the metal / resin composite structure 106, It is understood that the same evaluation result as the measurement point shown in FIG. 4 can be obtained even when the ten-point average roughness (Rz) and the average length of the roughness curve element (RSm) are measured.
（接合強度の評価方法および合否判定）
引っ張り試験機「モデル１３２３（アイコーエンジニヤリング社製）」を使用し、引張試験機に専用の治具を取り付け、室温（２３℃）にて、チャック間距離６０ｍｍ、引張速度１０ｍｍ／ｍｉｎの条件にて測定をおこなった。破断荷重（Ｎ）を金属／樹脂接合部分の面積で除することにより接合強度（ＭＰａ）を得た。
(Joint strength evaluation method and pass / fail judgment)
Using a tensile tester “Model 1323 (manufactured by Aiko Engineering Co., Ltd.)”, a dedicated jig is attached to the tensile tester, and at room temperature (23 ° C.), the distance between chucks is 60 mm and the tensile speed is 10 mm / min. And measured. The joint strength (MPa) was obtained by dividing the breaking load (N) by the area of the metal / resin joint.
（金属部材の表面粗化処理）
［金属部材１の調製方法］
ＪＩＳ Ｈ４０００に規定された合金番号５０５２のアルミニウム板（厚み：２．０ｍｍ）を、長さ４５ｍｍ、幅１８ｍｍに切断した。このアルミニウム板を酸系エッチング剤（硫酸：８．２質量％、塩化第二鉄：７．８質量％（Ｆｅ３＋：２．７質量％）、塩化第二銅：０．４質量％（Ｃｕ２＋：０．２質量％）イオン交換水：残部）（３０℃）中に８０秒間浸漬し、揺動させることによってエッチングした。次いで、流水で超音波洗浄（水中、１分）を行い、乾燥させることにより表面処理済みの金属部材１を得た。
(Surface roughening treatment of metal members)
[Method for Preparing Metal Member 1]
An aluminum plate (thickness: 2.0 mm) of alloy number 5052 defined in JIS H4000 was cut into a length of 45 mm and a width of 18 mm. This aluminum plate was treated with an acid-based etching agent (sulfuric acid: 8.2% by mass, ferric chloride: 7.8% by mass (Fe 3+ : 2.7% by mass), cupric chloride: 0.4% by mass (Cu Etching was performed by immersing in ( 2+ : 0.2% by mass) ion-exchanged water: remainder (30 ° C.) for 80 seconds and rocking. Next, ultrasonic cleaning (in water, 1 minute) was performed with running water, and the surface-treated metal member 1 was obtained by drying.
得られた金属部材１の間隔周期は、レーザー顕微鏡（ＫＥＹＥＮＣＥ社製ＶＫ−Ｘ１００）にて測定した。
また、得られた金属部材１の表面粗さを、表面粗さ測定装置「サーフコム１４００Ｄ（東京精密社製）」を使用して測定し、６直線部について、切断レベル１０％、２０％、３０％、４０％、５０％、６０％、７０％および８０％における負荷長さ率（Ｒｍｒ）、十点平均粗さ（Ｒｚ）および粗さ曲線要素の平均長さ（ＲＳｍ）を求めた。このうち、切断レベル２０％におけるＲｍｒ（２０％）値、上記Ｒｍｒ（２０％）値が３０％以下となる直線部の本数、切断レベル４０％におけるＲｍｒ（４０％）値、上記Ｒｍｒ（４０％）値が６０％以下となる直線部の本数、６直線部のＲｚ値、粗さ曲線要素の平均長さ（ＲＳｍ）、エッチング処理前後の金属部材の質量比から求めたエッチング率を算出した。
得られた結果を以下に示す。
The interval period of the obtained metal member 1 was measured with a laser microscope (VK-X100 manufactured by KEYENCE).
Further, the surface roughness of the obtained metal member 1 was measured using a surface roughness measuring device “Surfcom 1400D (manufactured by Tokyo Seimitsu Co., Ltd.)”, and cutting levels of 10%, 20%, and 30 were obtained for 6 straight portions. The load length ratio (Rmr), ten-point average roughness (Rz), and average length of the roughness curve element (RSm) at%, 40%, 50%, 60%, 70% and 80% were determined. Among these, the Rmr (20%) value at a cutting level of 20%, the number of straight portions where the Rmr (20%) value is 30% or less, the Rmr (40%) value at a cutting level of 40%, the Rmr (40%) ) The etching rate was calculated from the number of straight portions where the value was 60% or less, the Rz value of 6 straight portions, the average length (RSm) of the roughness curve elements, and the mass ratio of the metal members before and after the etching treatment.
The obtained results are shown below.
間隔周期［μｍ］：９２
切断レベル２０％におけるＲｍｒ（２０％）値：１７．５、１０．３、１３．４、１０．６、３．８、７．４
Ｒｍｒ（２０％）値が３０％以下となる直線部の本数：６
切断レベル４０％におけるＲｍｒ（４０％）値：４３．６、２６．１、４８．０、４６．７、３３．５、３４．２
Ｒｍｒ（４０％）値が６０％以下となる直線部の本数：６
６直線部のＲｚ値［μｍ］：１７．８、１８．１、１９．６、１７．８、１７．２、１８．０
６直線部のＲＳｍ値［μｍ］：１０４、８３．０、８５．６、９８．７、１０６．６、１０３．１
エッチング率［質量％］：２．６
Interval period [μm]: 92
Rmr (20%) value at 20% cutting level: 17.5, 10.3, 13.4, 10.6, 3.8, 7.4
Number of straight portions where the Rmr (20%) value is 30% or less: 6
Rmr (40%) values at 40% cleavage level: 43.6, 26.1, 48.0, 46.7, 33.5, 34.2
Number of straight portions where Rmr (40%) value is 60% or less: 6
Rz value [μm] of 6 linear portions: 17.8, 18.1, 19.6, 17.8, 17.2, 18.0
RSm value [μm] of 6 straight portions: 104, 83.0, 85.6, 98.7, 106.6, 103.1
Etching rate [% by mass]: 2.6
［金属部材２の調製方法］
ＪＩＳ Ｈ４０００に規定された合金番号５０５２のアルミニウム板（厚み：２．０ｍｍ）を、長さ４５ｍｍ、幅１８ｍｍに切断した。このアルミニウム板を特開２００５−１１９００５号公報の実施例１に記載の処理をおこなった。具体的には、市販のアルミニウム脱脂剤「ＮＥ−６（メルテックス社製）」を１５％濃度で水に溶かし７５℃とした。この水溶液が入ったアルミニウム脱脂槽に上記アルミニウム板を５分間浸漬し水洗し、４０℃の１％塩酸水溶液が入った槽に１分浸漬し水洗した。つづいて、４０℃の１％水酸化ナトリウム水溶液が入った槽に１分浸漬し水洗した。次いで４０℃の１％塩酸水溶液を入れた槽に１分浸漬し水洗し、６０℃の２．５％濃度の１水和ヒドラジン水溶液を入れた第１ヒドラジン処理槽に１分浸漬し、４０℃の０．５％濃度の１水和ヒドラジン水溶液を入れた第２ヒドラジン処理槽に０．５分浸漬し水洗した。これを４０℃で１５分間、６０℃で５分程度温風乾燥させることにより、表面処理済みの金属部材２を得た。
[Method for Preparing Metal Member 2]
An aluminum plate (thickness: 2.0 mm) of alloy number 5052 defined in JIS H4000 was cut into a length of 45 mm and a width of 18 mm. This aluminum plate was subjected to the treatment described in Example 1 of JP-A-2005-119005. Specifically, a commercially available aluminum degreasing agent “NE-6 (manufactured by Meltex)” was dissolved in water at a concentration of 15% to 75 ° C. The aluminum plate was immersed in an aluminum degreasing tank containing this aqueous solution for 5 minutes and washed with water, and then immersed in a tank containing a 1% hydrochloric acid aqueous solution at 40 ° C. for 1 minute and washed with water. Subsequently, it was immersed in a bath containing 1% sodium hydroxide aqueous solution at 40 ° C. for 1 minute and washed with water. Next, it was immersed in a bath containing 1% aqueous hydrochloric acid solution at 40 ° C. for 1 minute and washed with water, and immersed in a first hydrazine treatment bath containing a 2.5% strength monohydric hydrazine aqueous solution at 60 ° C. for 1 minute. Were immersed in a second hydrazine treatment tank containing a 0.5% strength monohydric hydrazine aqueous solution and washed with water. This was dried with warm air at 40 ° C. for 15 minutes and at 60 ° C. for about 5 minutes to obtain a surface-treated metal member 2.
得られた金属部材２の間隔周期は、走査型電子顕微鏡（ＪＥＯＬ社製ＪＳＭ−６７０１Ｆ）にて測定した。
また、エッチング処理前後の金属部材の質量比から求めたエッチング率を算出した。
得られた結果を以下に示す。
The interval period of the obtained metal member 2 was measured with a scanning electron microscope (JSMOL 6701F manufactured by JEOL).
Moreover, the etching rate calculated | required from the mass ratio of the metal member before and behind an etching process was computed.
The obtained results are shown below.
間隔周期［ｎｍ］：４５
エッチング率［質量％］：０．３
Interval period [nm]: 45
Etching rate [% by mass]: 0.3
［実施例１］
日本製鋼所社製の射出成形機Ｊ８５ＡＤに小型ダンベル金属インサート金型１０２を装着し、金型１０２内に金属部材１を設置した。次いで、高速ヒートサイクル成形用金型温調装置（Ｓｉｎｇｌｅ社製ＡＴＴ Ｈ２）を接続した金型１０２の表面温度を、加熱媒体である加圧熱水を用いて１１０℃まで加熱した。
次いで、その金型１０２内に、非晶性熱可塑性樹脂であるアクリロニトリル−ブタジエン−スチレン共重合体樹脂（ＡＢＳ樹脂）（日本エイ＆エル社製ＧＡ７０４、ガラス転移温度：１０５℃）を、シリンダー温度２６０℃、射出速度２５ｍｍ／ｓｅｃ、保圧９５ＭＰａ、保圧時間１５秒の条件にて射出成形を行い、次いで、保圧完了後、冷却媒体である水にて金型１０２の表面温度を４０℃まで急冷し、金属／樹脂複合構造体１０６を得た。接合強度の評価結果を表１に示す。
ここで、ＡＢＳ樹脂のガラス転移温度はＤＳＣ装置（ＴＡ Ｉｎｓｔｒｕｍｅｎｔｓ社製Ｑ２０００）にて、昇温速度１０℃／分の昇温過程により測定した値である。
[Example 1]
A small dumbbell metal insert mold 102 was mounted on an injection molding machine J85AD manufactured by Nippon Steel Works, and the metal member 1 was installed in the mold 102. Next, the surface temperature of the mold 102 connected to the high-speed heat cycle molding mold temperature controller (ATT H2 manufactured by Single Inc.) was heated to 110 ° C. using pressurized hot water as a heating medium.
Next, an acrylonitrile-butadiene-styrene copolymer resin (ABS resin) which is an amorphous thermoplastic resin (GA704 manufactured by Nippon A & L Inc., glass transition temperature: 105 ° C.) is placed in the mold 102 at a cylinder temperature. Injection molding is performed under the conditions of 260 ° C., injection speed of 25 mm / sec, holding pressure of 95 MPa, holding pressure of 15 seconds, and after completion of holding, the surface temperature of the mold 102 is set to 40 ° C. with water as a cooling medium. The metal / resin composite structure 106 was obtained. Table 1 shows the evaluation results of the bonding strength.
Here, the glass transition temperature of the ABS resin is a value measured by a DSC apparatus (Q2000 manufactured by TA Instruments) in a temperature rising process at a temperature rising rate of 10 ° C./min.
［実施例２〜３および比較例１］
射出開始から保圧完了までの間の金型１０２の表面温度および保圧完了後の金型１０２の表面温度を表１に示す値にそれぞれ変えた以外は実施例１と同様にして金属／樹脂複合構造体１０６を得た。接合強度の評価結果を表１に示す。
[Examples 2-3 and Comparative Example 1]
Metal / resin in the same manner as in Example 1 except that the surface temperature of the mold 102 from the start of injection to the completion of pressure holding and the surface temperature of the mold 102 after pressure holding were changed to the values shown in Table 1, respectively. A composite structure 106 was obtained. Table 1 shows the evaluation results of the bonding strength.
［実施例４］
日本製鋼所社製の射出成形機Ｊ８５ＡＤに小型ダンベル金属インサート金型１０２を装着し、金型１０２内に金属部材１を設置した。次いで、高速ヒートサイクル成形用金型温調装置（Ｓｉｎｇｌｅ社製ＡＴＴ Ｈ２）を接続した金型１０２の表面温度を、加熱媒体である加圧熱水を用いて１５５℃まで加熱した。
次いで、その金型１０２内に、非晶性熱可塑性樹脂であるポリカーボネート樹脂（ＰＣ樹脂）（帝人社製パンライトＬ１２２５Ｌ、ガラス転移温度：１４６℃）を、シリンダー温度３２０℃、射出速度２５ｍｍ／ｓｅｃ、保圧１００ＭＰａ、保圧時間１５秒の条件にて射出成形を行い、次いで、冷却媒体である水にて金型１０２の表面温度を６０℃まで急冷し、金属／樹脂複合構造体１０６を得た。接合強度の評価結果を表１に示す。
ここで、ＰＣ樹脂のガラス転移温度はＤＳＣ装置（ＴＡ Ｉｎｓｔｒｕｍｅｎｔｓ社製Ｑ２０００）にて、昇温速度１０℃／分の昇温過程により測定した値である。
[Example 4]
A small dumbbell metal insert mold 102 was mounted on an injection molding machine J85AD manufactured by Nippon Steel Works, and the metal member 1 was installed in the mold 102. Next, the surface temperature of the mold 102 connected to a high-temperature heat cycle molding mold temperature controller (ATT H2 manufactured by Single Corporation) was heated to 155 ° C. using pressurized hot water as a heating medium.
Next, a polycarbonate resin (PC resin) which is an amorphous thermoplastic resin (Teijin Panlite L1225L, glass transition temperature: 146 ° C.), cylinder temperature 320 ° C., injection speed 25 mm / sec, in the mold 102. Then, injection molding is performed under the conditions of a holding pressure of 100 MPa and a holding pressure time of 15 seconds, and then the surface temperature of the mold 102 is rapidly cooled to 60 ° C. with water as a cooling medium to obtain a metal / resin composite structure 106. It was. Table 1 shows the evaluation results of the bonding strength.
Here, the glass transition temperature of the PC resin is a value measured by a DSC apparatus (Q2000 manufactured by TA Instruments) in a temperature rising process at a temperature rising rate of 10 ° C./min.
［実施例５〜７、比較例２〜３］
金属部材の種類、射出開始から保圧完了までの間の金型１０２の表面温度、および保圧完了後の金型１０２の表面温度を表１に示す値にそれぞれ変えた以外は実施例４と同様にして金属／樹脂複合構造体１０６を得た。接合強度の評価結果を表１に示す。
[Examples 5-7, Comparative Examples 2-3]
Example 4 except that the type of metal member, the surface temperature of the mold 102 from the start of injection to the completion of holding pressure, and the surface temperature of the mold 102 after holding pressure were changed to the values shown in Table 1, respectively. Similarly, a metal / resin composite structure 106 was obtained. Table 1 shows the evaluation results of the bonding strength.
［実施例８］
日本製鋼所社製の射出成形機Ｊ８５ＡＤに小型ダンベル金属インサート金型１０２を装着し、金型１０２内に金属部材１を設置した。次いで、高速ヒートサイクル成形用金型温調装置（Ｓｉｎｇｌｅ社製ＡＴＴ Ｈ２）を接続した金型１０２の表面温度を、加熱媒体である加圧熱水を用いて１３０℃まで加熱した。
次いで、その金型１０２内に、非晶性熱可塑性樹脂であるポリメタクリル酸メチル樹脂（ＰＭＭＡ樹脂）（三菱レイヨン社製アクリペットＩＲＤ３０、ガラス転移温度：１０１℃）を、シリンダー温度２６０℃、射出速度２５ｍｍ／ｓｅｃ、保圧１１０ＭＰａ、保圧時間１５秒の条件にて射出成形を行い、次いで、冷却媒体である水にて金型１０２の表面温度を４０℃まで急冷し、金属／樹脂複合構造体１０６を得た。接合強度の評価結果を表１に示す。
ここで、ＰＭＭＡ樹脂のガラス転移温度はＤＳＣ装置（ＴＡ Ｉｎｓｔｒｕｍｅｎｔｓ社製Ｑ２０００）にて、昇温速度１０℃／分の昇温過程により測定した値である。
[Example 8]
A small dumbbell metal insert mold 102 was mounted on an injection molding machine J85AD manufactured by Nippon Steel Works, and the metal member 1 was installed in the mold 102. Next, the surface temperature of the mold 102 connected to the high-speed heat cycle molding mold temperature controller (ATT H2 manufactured by Single Inc.) was heated to 130 ° C. using pressurized hot water as a heating medium.
Next, an amorphous thermoplastic resin, polymethyl methacrylate resin (PMMA resin) (Acrypet IRD30 manufactured by Mitsubishi Rayon Co., Ltd., glass transition temperature: 101 ° C.) is injected into the mold 102 at a cylinder temperature of 260 ° C. Injection molding is carried out under the conditions of a speed of 25 mm / sec, a holding pressure of 110 MPa, and a holding pressure time of 15 seconds, and then the surface temperature of the mold 102 is rapidly cooled to 40 ° C. with water as a cooling medium, and a metal / resin composite structure A body 106 was obtained. Table 1 shows the evaluation results of the bonding strength.
Here, the glass transition temperature of the PMMA resin is a value measured by a DSC apparatus (Q2000 manufactured by TA Instruments) in a temperature rising process of 10 ° C./min.
［実施例９〜１１、比較例４〜５］
金属部材の種類、射出開始から保圧完了までの間の金型１０２の表面温度、および保圧完了後の金型１０２の表面温度を表１に示す値にそれぞれ変えた以外は実施例８と同様にして金属／樹脂複合構造体１０６を得た。接合強度の評価結果を表１に示す。
[Examples 9 to 11 and Comparative Examples 4 to 5]
Example 8 except that the type of metal member, the surface temperature of the mold 102 from the start of injection to the completion of holding pressure, and the surface temperature of the mold 102 after holding pressure were changed to the values shown in Table 1, respectively. Similarly, a metal / resin composite structure 106 was obtained. Table 1 shows the evaluation results of the bonding strength.
図５、６および７は、実施例１、実施例３および比較例１でそれぞれ作製した金属／樹脂複合構造体の接合部の電子顕微鏡写真（（ａ）倍率５００倍、（ｂ）倍率３０００倍）をそれぞれ示す図である。
実施例で得られた金属／樹脂複合構造体１０６は、図５および図６に示すように金属／樹脂複合構造体の接合部に観察される隙間が小さかった。すなわち、金属部材表面の微細凹凸形状の凹部の奥まで非晶性熱可塑性樹脂（Ａ）が侵入していた。これにより、得られた金属／樹脂複合構造体１０６は高い接合強度となったものと考えられる。
一方、比較例で得られた金属／樹脂複合構造体１０６は、図７に示すように金属／樹脂複合構造体の接合部に観察される隙間が大きかった。すなわち、金属部材表面の微細凹凸形状の凹部の奥まで非晶性熱可塑性樹脂（Ａ）が侵入していなかった。これにより、得られた金属／樹脂複合構造体１０６は実施例で得られたものよりも接合強度が低くなったと考えられる。
5, 6 and 7 are electron micrographs of the joints of the metal / resin composite structures produced in Example 1, Example 3 and Comparative Example 1, respectively ((a) magnification 500 times, (b) magnification 3000 times. ) Respectively.
As shown in FIGS. 5 and 6, the metal / resin composite structure 106 obtained in the example had a small gap observed at the joint of the metal / resin composite structure. That is, the amorphous thermoplastic resin (A) has penetrated to the back of the concave portion having a fine uneven shape on the surface of the metal member. Thereby, it is considered that the obtained metal / resin composite structure 106 has a high bonding strength.
On the other hand, in the metal / resin composite structure 106 obtained in the comparative example, as shown in FIG. 7, the gap observed at the joint of the metal / resin composite structure was large. That is, the amorphous thermoplastic resin (A) did not penetrate into the depths of the concave and convex portions on the surface of the metal member. Thereby, it is considered that the obtained metal / resin composite structure 106 has lower bonding strength than that obtained in the example.
１０１ 射出成形機
１０２ 金型
１０３ 金属部材
１０４ 接合部表面
１０５ 樹脂部材
１０６ 金属／樹脂複合構造体
１０７ ゲート／ランナー
１１０ 表面
DESCRIPTION OF SYMBOLS 101 Injection molding machine 102 Mold 103 Metal member 104 Joint surface 105 Resin member 106 Metal / resin composite structure 107 Gate / runner 110 Surface
Claims (10)
金型のキャビティ部に、間隔周期が５ｎｍ以上５００μｍ以下である凸部が林立した微細凹凸表面を有する前記金属部材を配置する工程と、
前記キャビティ部に前記樹脂組成物を射出することにより前記金属部材と前記樹脂部材とを接合する工程と、
を含み、
前記樹脂組成物の射出開始から保圧完了までの間、前記金型の表面温度を前記非晶性熱可塑性樹脂のガラス転移温度以上の温度に維持し、前記保圧完了後、前記金型の表面温度を前記非晶性熱可塑性樹脂のガラス転移温度未満の温度に冷却し、
前記金属部材の表面上の、平行関係にある任意の３直線部、および当該３直線部と直交する任意の３直線部からなる合計６直線部について、ＪＩＳ Ｂ０６０１（対応国際規格：ＩＳＯ４２８７）に準拠して測定される表面粗さが以下の要件（１）および（２）を同時に満たす金属／樹脂複合構造体の製造方法。
（１）切断レベル２０％、評価長さ４ｍｍにおける粗さ曲線の負荷長さ率（Ｒｍｒ）が３０％以下である直線部を１直線部以上含む
（２）すべての直線部の、評価長さ４ｍｍにおける十点平均粗さ（Ｒｚ）が２μｍを超える A manufacturing method for manufacturing a metal / resin composite structure formed by joining a metal member and a resin member made of a resin composition containing an amorphous thermoplastic resin,
A step of disposing the metal member having a fine concavo-convex surface in which convex portions having a spacing interval of 5 nm or more and 500 μm or less stand in a cavity portion of a mold;
Bonding the metal member and the resin member by injecting the resin composition into the cavity portion;
Including
During the period from the start of injection of the resin composition to the completion of pressure holding, the surface temperature of the mold is maintained at a temperature equal to or higher than the glass transition temperature of the amorphous thermoplastic resin. Cooling the surface temperature to a temperature below the glass transition temperature of the amorphous thermoplastic resin,
Conforms to JIS B0601 (corresponding international standard: ISO 4287) for a total of 6 straight line parts consisting of any 3 straight line parts in parallel relation on the surface of the metal member and any 3 straight line parts orthogonal to the 3 straight line parts. A method for producing a metal / resin composite structure in which the measured surface roughness satisfies the following requirements (1) and (2) simultaneously.
(1) Includes one or more straight line portions with a load length ratio (Rmr) of a roughness curve at a cutting level of 20% and an evaluation length of 4 mm of 30% or less. (2) Evaluation length of all straight line portions. Ten point average roughness (Rz) at 4 mm exceeds 2 μm
前記金型の表面の近くに設けられた流路に冷水および冷油から選択される冷却媒体を導入することにより、前記金型の前記表面温度を前記非晶性熱可塑性樹脂のガラス転移温度未満の温度に冷却する金属／樹脂複合構造体の製造方法。 In the manufacturing method of the metal / resin composite structure of Claim 1 ,
By introducing a cooling medium selected from cold water and cold oil into a flow path provided near the surface of the mold, the surface temperature of the mold is less than the glass transition temperature of the amorphous thermoplastic resin. The manufacturing method of the metal / resin composite structure cooled to the temperature of this.
前記金属部材の表面上の、平行関係にある任意の３直線部、および当該３直線部と直交する任意の３直線部からなる合計６直線部について、ＪＩＳ Ｂ０６０１（対応国際規格：ＩＳＯ４２８７）に準拠して測定される表面粗さが以下の要件（３）をさらに満たす金属／樹脂複合構造体の製造方法。
（３）切断レベル４０％、評価長さ４ｍｍにおける粗さ曲線の負荷長さ率（Ｒｍｒ）が６０％以下である直線部を１直線部以上含む In the manufacturing method of the metal / resin composite structure of Claim 1 or 2 ,
Conforms to JIS B0601 (corresponding international standard: ISO 4287) for a total of 6 straight line parts consisting of any 3 straight line parts in parallel relation on the surface of the metal member and any 3 straight line parts orthogonal to the 3 straight line parts. A method for producing a metal / resin composite structure, wherein the surface roughness measured by the method further satisfies the following requirement (3).
(3) One or more straight line portions having a load length ratio (Rmr) of a roughness curve at a cutting level of 40% and an evaluation length of 4 mm are 60% or less.
前記金属部材の表面上の、平行関係にある任意の３直線部、および当該３直線部と直交する任意の３直線部からなる合計６直線部について、すべての直線部の前記十点平均粗さ（Ｒｚ）が５μｍを超える金属／樹脂複合構造体の製造方法。 In the manufacturing method of the metal / resin composite structure as described in any one of Claims 1 thru | or 3 ,
The ten-point average roughness of all the straight portions of a total of six straight portions including arbitrary three straight portions in parallel relation on the surface of the metal member and arbitrary three straight portions orthogonal to the three straight portions. A method for producing a metal / resin composite structure in which (Rz) exceeds 5 μm.
前記金属部材の表面上の、平行関係にある任意の３直線部、および当該３直線部と直交する任意の３直線部からなる合計６直線部について、すべての直線部の前記十点平均粗さ（Ｒｚ）が１５μｍ以上である金属／樹脂複合構造体の製造方法。 In the manufacturing method of the metal / resin composite structure of Claim 4 ,
The ten-point average roughness of all the straight portions of a total of six straight portions including arbitrary three straight portions in parallel relation on the surface of the metal member and arbitrary three straight portions orthogonal to the three straight portions. A method for producing a metal / resin composite structure, wherein (Rz) is 15 μm or more.
前記金型の表面の近くに設けられた流路に水蒸気、温水および温油から選択される加熱媒体を導入する、あるいは電磁誘導加熱を用いることにより、前記金型の前記表面温度を前記非晶性熱可塑性樹脂のガラス転移温度以上の温度に維持する金属／樹脂複合構造体の製造方法。 In the manufacturing method of the metal / resin composite structure as described in any one of Claims 1 thru | or 5 ,
By introducing a heating medium selected from water vapor, hot water and hot oil into a flow path provided near the surface of the mold, or by using electromagnetic induction heating, the surface temperature of the mold is changed to the amorphous state. For producing a metal / resin composite structure, which is maintained at a temperature equal to or higher than the glass transition temperature of the thermoplastic resin.
前記射出開始から前記保圧完了までの時間が１秒以上４０秒以下である金属／樹脂複合構造体の製造方法。 In the manufacturing method of the metal / resin composite structure as described in any one of Claims 1 thru | or 6 ,
A method for producing a metal / resin composite structure, wherein the time from the start of injection to the completion of pressure holding is 1 second or more and 40 seconds or less.
前記非晶性熱可塑性樹脂が、ポリスチレン樹脂、ポリアクリロニトリル樹脂、スチレン−アクリロニトリル共重合体樹脂、アクリロニトリル−ブタジエン−スチレン共重合体樹脂、ポリメタクリル酸メチル樹脂、およびポリカーボネート樹脂から選択される一種または二種以上を含む金属／樹脂複合構造体の製造方法。 In the manufacturing method of the metal / resin composite structure as described in any one of Claims 1 thru | or 7 ,
The amorphous thermoplastic resin is one or two selected from polystyrene resin, polyacrylonitrile resin, styrene-acrylonitrile copolymer resin, acrylonitrile-butadiene-styrene copolymer resin, polymethyl methacrylate resin, and polycarbonate resin. A method for producing a metal / resin composite structure containing more than one species.
前記金属部材はアルミニウムおよびアルミニウム合金から選択される一種または二種以上の金属を含む金属材料からなる金属／樹脂複合構造体の製造方法。 In the manufacturing method of the metal / resin composite structure as described in any one of Claims 1 thru | or 8 ,
The said metal member is a manufacturing method of the metal / resin composite structure which consists of a metal material containing the 1 type, or 2 or more types of metal selected from aluminum and aluminum alloy.
前記非晶性熱可塑性樹脂のガラス転移温度をＴｇとしたとき、
前記樹脂組成物の前記射出開始から前記保圧完了までの間、前記金型の前記表面温度を前記非晶性熱可塑性樹脂のＴｇ＋（５以上１００以下）℃以上の温度に維持し、前記保圧完了後、前記金型の前記表面温度を前記非晶性熱可塑性樹脂のＴｇ−（５以上１００以下）℃以下の温度に冷却する金属／樹脂複合構造体の製造方法。
In the manufacturing method of the metal / resin composite structure as described in any one of Claims 1 thru | or 9 ,
When the glass transition temperature of the amorphous thermoplastic resin is Tg,
During the period from the start of injection of the resin composition to the completion of the pressure holding, the surface temperature of the mold is maintained at a temperature equal to or higher than Tg + (5 to 100) ° C of the amorphous thermoplastic resin. A method for producing a metal / resin composite structure, wherein the surface temperature of the mold is cooled to a temperature of Tg− (5 to 100) ° C. of the amorphous thermoplastic resin after completion of the pressing.
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