JP7405905B2 - A base material at least in whole or in part made of a metal material, the surface of the metal material having pores, and a composite of the base material and a cured resin material, including the base material and a cured resin material. - Google Patents
A base material at least in whole or in part made of a metal material, the surface of the metal material having pores, and a composite of the base material and a cured resin material, including the base material and a cured resin material. Download PDFInfo
- Publication number
- JP7405905B2 JP7405905B2 JP2022095125A JP2022095125A JP7405905B2 JP 7405905 B2 JP7405905 B2 JP 7405905B2 JP 2022095125 A JP2022095125 A JP 2022095125A JP 2022095125 A JP2022095125 A JP 2022095125A JP 7405905 B2 JP7405905 B2 JP 7405905B2
- Authority
- JP
- Japan
- Prior art keywords
- base material
- resin
- metal material
- metal
- cured resin
- 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.)
- Active
Links
- 239000000463 material Substances 0.000 title claims description 161
- 229920005989 resin Polymers 0.000 title claims description 84
- 239000011347 resin Substances 0.000 title claims description 84
- 239000007769 metal material Substances 0.000 title claims description 79
- 239000011148 porous material Substances 0.000 title claims description 42
- 239000002131 composite material Substances 0.000 title claims description 14
- 239000000805 composite resin Substances 0.000 claims description 23
- 238000011156 evaluation Methods 0.000 claims description 11
- 238000005520 cutting process Methods 0.000 claims description 10
- 239000002585 base Substances 0.000 description 122
- 238000000034 method Methods 0.000 description 63
- 238000011282 treatment Methods 0.000 description 39
- 239000000853 adhesive Substances 0.000 description 25
- 230000001070 adhesive effect Effects 0.000 description 25
- 238000004519 manufacturing process Methods 0.000 description 23
- -1 A5N01 Chemical compound 0.000 description 19
- 239000012756 surface treatment agent Substances 0.000 description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 16
- 239000007864 aqueous solution Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 16
- 239000007788 liquid Substances 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 229910052782 aluminium Inorganic materials 0.000 description 15
- 239000000758 substrate Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 13
- 230000002378 acidificating effect Effects 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000003513 alkali Substances 0.000 description 11
- 150000007522 mineralic acids Chemical class 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 238000001746 injection moulding Methods 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 229910052749 magnesium Inorganic materials 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 150000007524 organic acids Chemical class 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 229910000838 Al alloy Inorganic materials 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- 229910000881 Cu alloy Inorganic materials 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 239000004734 Polyphenylene sulfide Substances 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 238000005304 joining Methods 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 229920000069 polyphenylene sulfide Polymers 0.000 description 5
- 229920005992 thermoplastic resin Polymers 0.000 description 5
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 4
- 229910000861 Mg alloy Inorganic materials 0.000 description 4
- 229910001069 Ti alloy Inorganic materials 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 238000003486 chemical etching Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229920002725 thermoplastic elastomer Polymers 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- 239000002905 metal composite material Substances 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000007788 roughening Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000004094 surface-active agent Substances 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
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 229910000640 Fe alloy Inorganic materials 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000005422 blasting Methods 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000001493 electron microscopy Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000000174 gluconic acid Substances 0.000 description 2
- 235000012208 gluconic acid Nutrition 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000008235 industrial water Substances 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical class [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 235000012254 magnesium hydroxide Nutrition 0.000 description 2
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 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
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-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
- 229920000178 Acrylic resin Polymers 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 101001108245 Cavia porcellus Neuronal pentraxin-2 Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 101150000971 SUS3 gene Proteins 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 238000003483 aging Methods 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000010407 anodic oxide Substances 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- VNTLIPZTSJSULJ-UHFFFAOYSA-N chromium molybdenum Chemical compound [Cr].[Mo] VNTLIPZTSJSULJ-UHFFFAOYSA-N 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 239000013527 degreasing agent Substances 0.000 description 1
- 238000005237 degreasing agent Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000004093 laser heating Methods 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000001139 pH measurement Methods 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 102200082816 rs34868397 Human genes 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007660 shear property test Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- C—CHEMISTRY; METALLURGY
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Laminated Bodies (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- ing And Chemical Polishing (AREA)
Description
本発明は、少なくとも表面の全部又は一部が金属材料からなる基材であって、前記金属材料の表面が特定の孔を有する基材と、該基材と樹脂硬化物を含む基材－樹脂硬化物の複合体に関する。 The present invention provides a base material at least in whole or in part made of a metal material, the surface of the metal material having specific pores, and a base material containing the base material and a cured resin material. The present invention relates to a composite of a cured product.
金属材料と樹脂を接合する方法の一つとして、金属材料表面を粗化処理した後に樹脂をインサート成形する方法が知られている。例えば、特許文献１には以下のように記載されている。 As one of the methods for joining a metal material and a resin, a method is known in which the surface of the metal material is roughened and then a resin is insert-molded. For example, Patent Document 1 describes as follows.
金属部材と、熱可塑性樹脂組成物からなる樹脂部材とが接合してなる金属／樹脂複合構造体であって、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、及び当該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）及び（２）を同時に満たす金属／樹脂複合構造体。
（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 metal/resin composite structure formed by bonding a metal member and a resin member made of a thermoplastic resin composition, wherein any three linear portions in a parallel relationship on the surface of the metal member, and the three The surface roughness measured in accordance with JIS B0601 (corresponding international standard: ISO4287) for a total of 6 straight sections consisting of 3 arbitrary straight sections perpendicular to the straight section satisfies the following requirements (1) and (2) at the same time. Metal/resin composite structure.
(1) Includes at least one straight section where the load length ratio (Rmr) of the roughness curve at a cutting level of 20% and an evaluation length of 4 mm is 30% or less. (2) Evaluation length of all straight sections Ten point average roughness (Rz) at 4mm exceeds 2μm
本発明者らの検討によれば、特許文献１に開示されている方法で得られた金属／樹脂複合構造体の接合強度は、不十分な場合があった。 According to studies by the present inventors, the bonding strength of the metal/resin composite structure obtained by the method disclosed in Patent Document 1 was sometimes insufficient.
本発明は、上記の従来技術の問題を解決すること、すなわち、樹脂との接合強度に優れる特定の孔を有する金属材料を有する基材及び前記基材と樹脂硬化物を含む基材－樹脂硬化物の複合体を提供することを目的とする。 The present invention solves the above-mentioned problems of the prior art, that is, a base material having a metal material having a specific hole that has excellent bonding strength with a resin, and a base material containing the base material and a cured resin product - cured resin. The purpose is to provide a complex of things.
本発明者らは、上記課題を解決するために鋭意検討した結果、少なくとも表面の全部又は一部が金属材料からなる基材であって、前記金属材料の表面が特定の孔を有する基材を見出し、本発明を完成するに至った。
すなわち、本発明の主旨は以下のとおりである。
As a result of intensive studies to solve the above problems, the present inventors have discovered that a base material at least in whole or in part on its surface is made of a metal material, and in which the surface of the metal material has specific pores. This discovery led to the completion of the present invention.
That is, the gist of the present invention is as follows.
［１］少なくとも表面の全部又は一部が金属材料からなる基材であって、該金属材料の表面が孔を有し、以下の（１）及び（２）の要件を満たす、基材。
（１）断面曲線の負荷長さ率(Ｐｍｒ)が切断レベル３０％、評価長さ１０μｍにおいて４０％以上である
（２）孔の入口における直径の平均値（ａ）と、孔深さの平均値（ｂ）とのアスペクト比（ｂ／ａ）が２以上５０以下である
［２］基材と樹脂硬化物を含む基材－樹脂複合体であって、該基材が［１］に記載の基材
であり、該基材が有する金属材料の表面における孔に、樹脂硬化物を含む、基材－樹脂硬化物の複合体。
[1] A base material in which at least all or part of the surface is made of a metal material, the surface of the metal material has pores, and satisfies the following requirements (1) and (2).
(1) The load length ratio (Pmr) of the cross-sectional curve is 40% or more at the cutting level of 30% and the evaluation length of 10 μm. (2) The average value of the diameter at the entrance of the hole (a) and the average of the hole depth Aspect ratio (b/a) of value (b) is 2 or more and 50 or less [2] A base material-resin composite comprising a base material and a cured resin, the base material described in [1] A composite of a base material and a cured resin material, which is a base material, and contains a cured resin material in the pores on the surface of a metal material that the base material has.
本発明によれば、樹脂との接合強度に優れる、少なくとも表面の全部又は一部が金属材料からなる基材であって、前記金属材料の表面が特定の孔を有する基材及び前記基材と樹脂硬化物を含む基材－樹脂硬化物の複合体を提供することができる。 According to the present invention, there is provided a base material having excellent bonding strength with a resin, at least the whole or part of the surface of which is made of a metal material, the surface of the metal material having specific holes, and the base material. A composite of a substrate containing a cured resin and a cured resin can be provided.
以下、本発明について詳細に説明する。
なお、本明細書において、「孔」とは貫通孔ではなく、凹みを形成するものを意味する。
The present invention will be explained in detail below.
In addition, in this specification, a "hole" does not mean a through hole but a hole forming a recess.
＜少なくとも表面の全部又は一部が金属材料からなる基材＞
本発明の実施形態に適用される基材は、少なくとも表面の全部又は一部が金属材料からなる基材であれば特に制限されない。
基材の少なくとも表面の全部又は一部に存在する金属材料は、鉄、鉄合金、チタン、チタン合金、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、銅合金等を挙げることができるが、特に限定されない。基材は、特に限定されず、展伸材、押出材、鋳造材、ダイカスト材を含む。前記金属材料は、単独で用いてもよいし、二種類以上の金属材料を組み合わせて使用してもよい。これらの金属材料の中でも、軽量かつ高強度の観点から、アルミニウム又はアルミニウム合金が好ましい。以後、アルミニウム又はアルミニウム合金を単に「アルミニウム材」と称することもある。
<Base material at least the whole or part of the surface is made of a metal material>
The base material applied to the embodiments of the present invention is not particularly limited as long as at least all or part of the surface thereof is made of a metal material.
Examples of the metal material present on all or part of at least the surface of the base material include iron, iron alloy, titanium, titanium alloy, aluminum, aluminum alloy, magnesium, magnesium alloy, copper, copper alloy, etc. Not limited. The base material is not particularly limited, and includes a wrought material, an extruded material, a cast material, and a die-cast material. The metal materials may be used alone or in combination of two or more types of metal materials. Among these metal materials, aluminum or aluminum alloy is preferred from the viewpoint of light weight and high strength. Hereinafter, aluminum or aluminum alloy may be simply referred to as "aluminum material".
鉄又は鉄合金は、特に限定されず、産業上使用される普通鋼、クロムモリブデン鋼、ステンレス鋼などが挙げられる。具体的には、ＪＩＳＧ ４０５１、ＪＩＳ Ｇ ４０５３、
ＪＩＳ Ｇ４３０４などに規格されたＳ４５Ｃ、ＳＣＭ４１５、ＳＵＳ３０４、ＳＵＳ３
１６、ＳＵＳ４３０などが挙げられる。
The iron or iron alloy is not particularly limited, and includes industrially used ordinary steel, chromium molybdenum steel, stainless steel, and the like. Specifically, JIS G 4051, JIS G 4053,
S45C, SCM415, SUS304, SUS3 standardized to JIS G4304 etc.
16, SUS430, etc.
チタン又はチタン合金は、特に限定されず、産業上使用される純チタン、α－β合金、β合金などが挙げられる。具体的にはＪＩＳＨ ４６００に規格された１種から４種の純
チタン、Ｔｉ－６Ａｌ－４Ｖ、Ｔｉ－２２Ｖ－４Ａｌなどのチタン合金が挙げられる。
Titanium or titanium alloy is not particularly limited, and includes industrially used pure titanium, α-β alloy, β alloy, and the like. Specifically, titanium alloys such as pure titanium of types 1 to 4 specified by JISH 4600, Ti-6Al-4V, and Ti-22V-4Al can be mentioned.
アルミニウム又はアルミニウム合金は、特に限定されず、産業上使用されるいずれのアルミニウム材も適用できる。アルミニウム材とは、アルミニウムを６０％以上含む材料を指し、アルミニウム以外の合金成分としては、例えば、マグネシウム、ケイ素、チタン、クロム、マンガン、鉄、ニッケル、銅、亜鉛を挙げることができる。具体的には、例えば、ＪＩＳ Ｈ ４０００、ＪＩＳ Ｈ ５３０２及びＪＩＳ Ｈ ５２０２に規格されたＡ１０５０、Ａ２０１４、Ａ２０２４、Ａ３００３、Ａ５０５２、Ａ５Ｎ０１、Ａ６０６１、Ａ６０６３、Ａ７０７５、ＡＣ４Ａ、ＡＤＣ１２などが挙げられる。 Aluminum or aluminum alloy is not particularly limited, and any industrially used aluminum material can be applied. The aluminum material refers to a material containing 60% or more of aluminum, and alloy components other than aluminum include, for example, magnesium, silicon, titanium, chromium, manganese, iron, nickel, copper, and zinc. Specifically, examples thereof include A1050, A2014, A2024, A3003, A5052, A5N01, A6061, A6063, A7075, AC4A, and ADC12, which are standardized in JIS H 4000, JIS H 5302, and JIS H 5202.
マグネシウム合金は、特に限定されず、産業上使用されるいずれのマグネシウム合金も
適用できる。そのマグネシウム合金の具体例としては、ＡＺ９２、ＡＺ９１、ＡＺ８０、ＡＺ６３、ＡＺ６１、ＡＺ３１、ＡＭ１００、ＡＭ６０、ＡＭ５０、ＡＭ２０、ＡＳ４１、ＡＳ２１、ＡＥ４２、ＡＣＭ５２２等が挙げられる。
The magnesium alloy is not particularly limited, and any industrially used magnesium alloy can be used. Specific examples of the magnesium alloy include AZ92, AZ91, AZ80, AZ63, AZ61, AZ31, AM100, AM60, AM50, AM20, AS41, AS21, AE42, ACM522, and the like.
銅又は銅合金は、特に限定されず、産業上使用されるいずれの銅又は銅合金も適用できる。銅又は銅合金の具体例としては、ＪＩＳ Ｈ ３１００に規格されたＣ１０２０、Ｃ１１００、Ｃ１２２０、Ｃ２８０１、Ｃ４６２１、Ｃ６１４０などが挙げられる。 Copper or copper alloy is not particularly limited, and any industrially used copper or copper alloy can be applied. Specific examples of copper or copper alloys include C1020, C1100, C1220, C2801, C4621, and C6140, which are standardized in JIS H 3100.
少なくとも表面の全部又は一部が金属材料からなる基材の形状は、樹脂が接合できる形状であれば特に限定されず、例えば、板、棒、帯、管、線、繊維、箔、塊であってもよい。また、これらを組み合わせた構造体であってもよい。なお、前記基材は中間製品、完成品の全てが本発明の実施形態にかかる基材の範疇に含まれる。前記基材の少なくとも表面の全部又は一部が金属材料であれば、それ以外の部分は金属材料以外の材料であってもよい。もちろん金属材料のみから基材が構成されてもよい。金属材料以外の材料とは、例えば、前記基材以外の金属、樹脂、ゴム、木材、セラミック、複合材料等が挙げられるが、これらに限定されない。前記基材以外の材料の接合方法は特に限定されない。また、樹脂と接合する、基材が有する金属材料の接合部表面の形状は、平面や曲面等が挙げられるが特に限定されない。 The shape of the base material, at least a part of which is made of a metal material, is not particularly limited as long as it can be bonded with resin; for example, it may be a plate, rod, band, tube, wire, fiber, foil, or lump. You can. Alternatively, a structure may be a combination of these. It should be noted that both intermediate products and finished products are included in the category of the base material according to the embodiment of the present invention. As long as at least all or part of the surface of the base material is made of a metal material, the other portions may be made of a material other than the metal material. Of course, the base material may be composed only of a metal material. Examples of materials other than metal materials include, but are not limited to, metals other than the base material, resins, rubber, wood, ceramics, composite materials, and the like. The method of joining materials other than the base material is not particularly limited. Further, the shape of the joint surface of the metal material of the base material, which is joined to the resin, may be a flat surface or a curved surface, but is not particularly limited.
前記基材は、塑性加工、切削加工、ブラスト加工、研磨加工、放電加工、穴あけ加工、熱処理（時効硬化処理、溶体化処理など）が施されていてもよい。また、前記基材は、表面処理（化成処理、めっき処理、陽極酸化処理など）が施されていてもよいが、下記で説明する孔を形成する前に研磨や化学処理等によってこれらの皮膜成分を除去することが好ましい。 The base material may be subjected to plastic working, cutting, blasting, polishing, electric discharge machining, drilling, or heat treatment (age hardening treatment, solution treatment, etc.). Further, the base material may be subjected to surface treatment (chemical conversion treatment, plating treatment, anodization treatment, etc.), but before forming the pores described below, these coating components are removed by polishing, chemical treatment, etc. It is preferable to remove.
本発明の実施形態に係る、少なくとも表面の全部又は一部が金属材料からなる基材は、該金属材料の表面が孔を有し、以下の（１）及び（２）の要件を満たす。
（１）断面曲線の負荷長さ率(Ｐｍｒ)が切断レベル３０％、評価長さ１０μｍにおいて４０％以上である
（２）孔の入口における直径の平均値（ａ）と、孔深さの平均値（ｂ）とのアスペクト比（ｂ／ａ）が２以上５０以下である
In the base material according to the embodiment of the present invention, at least the whole or part of the surface of which is made of a metal material, the surface of the metal material has holes and satisfies the following requirements (1) and (2).
(1) The load length ratio (Pmr) of the cross-sectional curve is 40% or more at the cutting level of 30% and the evaluation length of 10 μm. (2) The average value of the diameter at the entrance of the hole (a) and the average of the hole depth The aspect ratio (b/a) to the value (b) is 2 or more and 50 or less
これにより、前記孔を有する金属材料を有する基材を、基材－樹脂硬化物の複合体の製造に用いた場合、樹脂との接合強度が優れた複合体を形成することができる。断面曲線の負荷長さ率が上記下限値未満であると、上記強度が低下するため樹脂との接合強度が低下する。断面曲線の負荷長さ率は、より好ましくは４５％以上であり、さらに好ましくは５０％以上である。断面曲線の負荷長さ率の上限については特に制限はないが、負荷長さ率が高すぎると金属表面に存在する孔の割合が少なく、樹脂との優れた接合強度が得られないという観点から、通常、９５％以下である。
また、アスペクト比が２未満の場合、樹脂との接合強度は低下する。
断面曲線の負荷長さ率が上記下限値以上であっても、アスペクト比が２未満の場合は、樹脂との優れた接合強度が得られない。また、アスペクト比が２以上であっても断面曲線の負荷長さ率が上記下限値未満であると、上記強度が低下するため、優れた接合強度が得られない。
したがって、樹脂との優れた接合強度を得るためには、前記（１）及び（２）の２つの要件を同時に満たすことが必要である。
As a result, when the base material having the metal material having holes is used for manufacturing a base material-resin cured product composite, it is possible to form a composite with excellent bonding strength with the resin. If the load length ratio of the cross-sectional curve is less than the above lower limit value, the above strength will decrease, and therefore the bonding strength with the resin will decrease. The load length ratio of the cross-sectional curve is more preferably 45% or more, and even more preferably 50% or more. There is no particular restriction on the upper limit of the load length ratio of the cross-sectional curve, but from the viewpoint that if the load length ratio is too high, the proportion of pores existing on the metal surface will be small and excellent bonding strength with the resin will not be obtained. , usually 95% or less.
Moreover, when the aspect ratio is less than 2, the bonding strength with the resin decreases.
Even if the load length ratio of the cross-sectional curve is at least the above lower limit, if the aspect ratio is less than 2, excellent bonding strength with the resin cannot be obtained. Further, even if the aspect ratio is 2 or more, if the load length ratio of the cross-sectional curve is less than the above lower limit, the above strength decreases, and excellent bonding strength cannot be obtained.
Therefore, in order to obtain excellent bonding strength with the resin, it is necessary to simultaneously satisfy the two requirements (1) and (2).
本発明の実施形態に係る孔を有する金属材料の断面曲線の負荷長さ率及びアスペクト比の測定方法を以下に説明する。 A method for measuring the load length ratio and aspect ratio of a cross-sectional curve of a metal material having holes according to an embodiment of the present invention will be described below.
（断面曲線の負荷長さ率（Ｐｍｒ(ｃ)））
断面曲線の負荷長さ率（Ｐｍｒ(ｃ)）は、式（Ａ）に示すように、評価長さ（ｌｎ）に対する切断レベルｃにおける輪郭曲線要素の負荷長さＭｌ（ｃ）の比を表したものであり、その測定方法はＪＩＳ Ｂ ０６０１に規定されている。
（Ａ） Ｐｍｒ(ｃ) ＝ Ｍｌ（ｃ）／ ｌｎ
しかしながら、本発明の実施形態に係る孔の形状は市販の表面粗さ計等では正確に測定することが困難である。したがって、本発明の実施形態における断面曲線の負荷長さ率は、孔を有する金属材料を有する基材の実表面に対して垂直方向に切断したとき、その切り口に現れる断面構造を電子顕微鏡観察で撮影した写真から測定する。断面構造を観察するための試料の作製方法は、特に限定されないが、例えば、機械研磨法、集束イオンビーム法、イオンミリング法、ミクロトーム法などが挙げられる。要するに、孔の構造が観察できればよい。
(Load length ratio of cross-sectional curve (Pmr(c)))
The load length ratio (Pmr(c)) of the cross-sectional curve represents the ratio of the load length Ml(c) of the contour curve element at the cutting level c to the evaluation length (ln), as shown in equation (A). The measurement method is specified in JIS B 0601.
(A) Pmr(c) = Ml(c)/ln
However, it is difficult to accurately measure the shape of the pores according to the embodiments of the present invention using a commercially available surface roughness meter. Therefore, the load length ratio of the cross-sectional curve in the embodiment of the present invention is determined by electron microscopy of the cross-sectional structure that appears at the cut when a base material containing a metal material with holes is cut in a direction perpendicular to the actual surface. Measure from the photo taken. A method for preparing a sample for observing a cross-sectional structure is not particularly limited, and examples thereof include a mechanical polishing method, a focused ion beam method, an ion milling method, a microtome method, and the like. In short, it is sufficient if the structure of the pores can be observed.
図１に示した表面に孔を有する金属材料を有する基材の断面模式図において、この厚さ方向に直交し、かつ凹凸部の最高部を通過するトップラインと最深部を通過するボトムラインの距離をＲｔとする。本発明の実施形態においては切断レベルｃを３０％と設定する。つまり、Ｒｔに対してトップラインから３０％の高さが切断レベルである。本発明の実施形態においては、評価長さは１０μｍに設定する。負荷長さＭｌ（ｃ）は、電子顕微鏡で撮影した写真から切断レベル３０％によって切断された輪郭曲線要素の実体側の長さ（図１においてはＭｌ１からＭｌ９）の和を測定することにより求めることができる。
したがって、本発明の実施形態における断面曲線の負荷長さ率とは、孔を有する金属材料を有する基材の実表面に対して垂直方向に切断したとき、その切り口に現れる断面構造を電子顕微鏡で撮影した写真において、Ｒｔに対してトップラインから３０％の高さにおける負荷長さＭｌ（ｃ）の評価長さ１０μｍに対する比率を表したものである。断面曲線の負荷長さ率を求めるためには、電子顕微鏡観察において倍率を１万倍以上にすることが好適である。
In the schematic cross-sectional view of a base material having a metal material with holes on its surface shown in FIG. Let the distance be Rt. In the embodiment of the present invention, the cutting level c is set to 30%. That is, a height of 30% from the top line with respect to Rt is the cutting level. In the embodiment of the present invention, the evaluation length is set to 10 μm. The load length Ml (c) is determined by measuring the sum of the lengths of the real side of the contour curve elements (from Ml 1 to Ml 9 in FIG. 1) cut at a cutting level of 30% from a photograph taken with an electron microscope. It can be found by
Therefore, the load length ratio of the cross-sectional curve in the embodiment of the present invention refers to the cross-sectional structure that appears at the cut end when a base material containing a metal material with holes is cut in a direction perpendicular to the actual surface. In the photograph taken, the ratio of the load length Ml(c) at a height of 30% from the top line with respect to Rt to the evaluation length of 10 μm is expressed. In order to determine the load length ratio of the cross-sectional curve, it is preferable to use a magnification of 10,000 times or more in electron microscope observation.
（アスペクト比）
本発明の実施形態に係るアスペクト比は、孔の入口における直径の平均値（ａ）と、孔の深さの平均値（ｂ）の比（ｂ／ａ）により算出される。アスペクト比が２以上とは、前記（ｂ）が前記（ａ）の２倍以上の孔深さの平均値を有する孔が存在することを意味する。孔の入口における直径の平均値は、孔を有する金属材料を有する基材の表面を電子顕微鏡で撮影した写真から測定可能である。本発明の実施形態に係る基材が有する金属材料の表面には、図２に示すように円形又は楕円形の孔が観察される。本発明の実施形態に係る孔の入口における直径の平均値は、表面に形成されている円形又は楕円形の開口部の直径（図２のａ）又は短径（図２のｂ）の平均値であり、開口部の直径又は短径の長いものから上位２割の孔を選択し、それらの長さを測定し、全てを積算してその上位２割の孔の数で除したものを孔の入口における直径の平均値とする。孔の直径を求めるためには、電子顕微鏡観察において倍率を１万倍以上にすることが好適である。
(aspect ratio)
The aspect ratio according to the embodiment of the present invention is calculated by the ratio (b/a) of the average value of the diameter at the entrance of the hole (a) and the average value of the depth of the hole (b). The aspect ratio of 2 or more means that there are pores in which the average depth of the pores in (b) is twice or more than that in (a). The average value of the diameter at the entrance of the pores can be measured from a photograph taken with an electron microscope of the surface of the base material having the metal material having the pores. As shown in FIG. 2, circular or elliptical holes are observed on the surface of the metal material of the base material according to the embodiment of the present invention. The average value of the diameter at the entrance of the hole according to the embodiment of the present invention is the average value of the diameter (a in FIG. 2) or the short axis (b in FIG. 2) of the circular or elliptical opening formed on the surface. Select the top 20% of the holes with the longest opening diameter or short axis, measure their lengths, add up all of them, and divide by the number of holes in the top 20%. The average value of the diameter at the entrance of In order to determine the diameter of the pores, it is preferable to use an electron microscope at a magnification of 10,000 times or more.
孔の入口における直径の平均値は、多数の孔を測定対象とする場合には、前記基材の実表面に対して垂直方向に切断したとき、その切り口に現れる断面構造を電子顕微鏡で撮影した写真からも測定可能である。その場合、孔の入口における直径の平均値は、形成されている孔の最上部の開口幅（図３のｃ）の平均値であり、開口幅の長いものから上位１０個を選択し、それらの長さを測定し、全てを積算して１０で除したものを孔の入口における直径の平均値とする。孔の直径を求めるためには、電子顕微鏡観察において倍率を１万倍以上にすることが好適である。孔の入口における直径の平均値の測定方法は、孔を有する金属材料を有する基材の表面を電子顕微鏡で撮影した写真から求めるほうがより好ましい。 When a large number of holes are to be measured, the average value of the diameter at the entrance of the pores can be determined by taking an electron microscope image of the cross-sectional structure that appears at the cut end when the base material is cut in a direction perpendicular to the actual surface. It can also be measured from photographs. In that case, the average value of the diameter at the entrance of the hole is the average value of the opening width at the top of the hole being formed (c in Figure 3), and the top 10 holes with the longest opening width are selected and Measure the lengths of the holes, add them all up, divide by 10, and take the average value of the diameter at the entrance of the hole. In order to determine the diameter of the pores, it is preferable to use an electron microscope at a magnification of 10,000 times or more. As for the method of measuring the average value of the diameter at the entrance of the pores, it is more preferable to determine it from a photograph taken with an electron microscope of the surface of the base material having the metal material having the pores.
孔深さの平均値は、前記基材の実表面に対して垂直方向に切断したとき、その切り口に現れる断面構造を電子顕微鏡観察で撮影した写真から測定する。孔深さを求めるためには、電子顕微鏡観察において倍率を1万倍以上にすることが好適である。
孔深さの平均値は、形成されている孔における最上部から最深部の間の長さ（図３のｄ）の平均値であり、孔深さの長いものから上位１０個を選択し、それらの最上部から最深部の長さを測定し、全てを積算して１０で除したものを孔深さの平均値とする。
The average value of the pore depth is measured from a photograph taken by electron microscopy of the cross-sectional structure appearing at the cut end when the base material is cut in a direction perpendicular to the actual surface. In order to determine the hole depth, it is preferable to use an electron microscope at a magnification of 10,000 times or more.
The average value of the hole depth is the average value of the length between the top and the deepest part (d in Figure 3) of the holes being formed, and the top 10 holes with the longest hole depth are selected, Measure the length from the top to the deepest part, integrate all the lengths, and divide by 10 to obtain the average hole depth.
本発明の実施形態に係る孔を有する金属材料を有する基材と樹脂との接合強度をより一層向上させる観点から、前記基材の孔の入口における直径の範囲は、好ましくは５０ｎｍ以上４０００ｎｍ以下であり、より好ましくは６０ｎｍ以上２０００ｎｍ以下であり、さらに好ましくは７０ｎｍ以上１０００ｎｍ以下である。 From the viewpoint of further improving the bonding strength between the resin and the base material having a metal material having pores according to the embodiment of the present invention, the diameter range at the entrance of the pores of the base material is preferably 50 nm or more and 4000 nm or less. It is more preferably 60 nm or more and 2000 nm or less, and even more preferably 70 nm or more and 1000 nm or less.
本発明の実施形態に係る孔を有する金属材料を有する基材と樹脂との接合強度をより一層向上させる観点から、前記基材の孔深さの範囲は、好ましくは１００ｎｍ以上１０μｍ以下であり、より好ましくは２００ｎｍ以上９μｍ以下であり、さらに好ましくは３００ｎｍ以上８μｍ以下である。 From the viewpoint of further improving the bonding strength between the resin and the base material having a metal material having holes according to the embodiment of the present invention, the depth of the holes in the base material preferably ranges from 100 nm to 10 μm, More preferably, it is 200 nm or more and 9 μm or less, and even more preferably 300 nm or more and 8 μm or less.
本発明の実施形態に係る上記（２）で規定されるアスペクト比は、２以上５０以下である。本発明の実施形態に係る孔を有する金属材料を有する基材と樹脂との接合強度をより一層向上させる観点から、前記アスペクト比の範囲は、２以上であり、好ましくは３以上であり、さらに好ましくは４以上である。前記アスペクト比が５０を超える場合、金属材料自身の強度が低下する。 The aspect ratio defined in (2) above according to the embodiment of the present invention is 2 or more and 50 or less. From the viewpoint of further improving the bonding strength between the base material having the metal material having holes according to the embodiment of the present invention and the resin, the aspect ratio range is 2 or more, preferably 3 or more, and Preferably it is 4 or more. When the aspect ratio exceeds 50, the strength of the metal material itself decreases.
前記孔は、前記基材の表面及び断面の任意の１０箇所を観察して1箇所以上確認できれ
ばよい。
より具体的には、本発明の実施形態において、金属材料の表面における、前記アスペクト比を有する孔の数は、金属材料の表面の面積１μｍ２あたり、１個以上を有することが好ましく、２個以上有することがより好ましい。
前記孔は、前記基材の全面に存在する必要はなく、少なくとも後述する樹脂と接合する部分が有していればよい。
It is sufficient that one or more holes can be confirmed by observing ten arbitrary points on the surface and cross section of the base material.
More specifically, in the embodiment of the present invention, the number of holes having the aspect ratio on the surface of the metal material is preferably one or more per 1 μm 2 of the surface area of the metal material, and preferably 2 or more. It is more preferable to have the above.
The holes do not need to be present on the entire surface of the base material, and it is sufficient that the holes are present at least in the portion to be bonded to the resin described below.
＜孔を有する金属材料を有する基材の製造方法＞
次に、本発明の実施形態に係る孔を有する金属材料を有する基材の製造方法（以下、孔形成工程と称することもある）について説明する。
本発明の実施形態において、前記の孔を有する金属材料を有する基材を製造する方法は、特に限定されず、インプリント法、レーザー加工法、化学エッチング法などの公知の方法が挙げられる。インプリント法は、複数の突起を有する基板又はロールを、金属材料を有する基材に押し付けて孔を形成する方法であり、転写法やプレスパターニング法などが挙げられる。レーザー加工法は、金属材料の表面にレーザー光を照射して孔を形成させる方法である。化学エッチング法は、化学薬品を用いた処理液に金属材料を有する基材を接触させることにより腐食を進行させ、孔を形成させる方法である。
本発明の実施形態に係る孔形成工程においては、皮膜形成による孔の作製方法は除く。皮膜としては、陽極酸化皮膜、化成皮膜（リン酸塩系皮膜、ジルコニウム系皮膜、クロム系皮膜、ケイ酸塩皮膜、リチウム系化成皮膜）、めっき膜等が挙げられる。
<Method for manufacturing base material having metal material with holes>
Next, a method for manufacturing a base material having a metal material having holes (hereinafter sometimes referred to as a hole forming step) according to an embodiment of the present invention will be described.
In the embodiment of the present invention, the method for producing the base material having the metal material having holes is not particularly limited, and includes known methods such as an imprint method, a laser processing method, and a chemical etching method. The imprint method is a method of forming holes by pressing a substrate or roll having a plurality of protrusions against a base material having a metal material, and examples thereof include a transfer method and a press patterning method. The laser processing method is a method of forming holes by irradiating the surface of a metal material with laser light. The chemical etching method is a method in which a base material containing a metal material is brought into contact with a treatment solution using chemicals to advance corrosion and form holes.
In the hole forming step according to the embodiment of the present invention, a method for forming holes by film formation is excluded. Examples of the film include anodized films, chemical conversion films (phosphate-based films, zirconium-based films, chromium-based films, silicate films, lithium-based chemical conversion films), plating films, and the like.
本発明の実施形態において、前記孔を有する基材を製造する方法として、以下に示す化学エッチング法が好適である。この化学エッチング法は、少なくとも表面の全部又は一部にアルミニウム材を有する基材の製造に対して特に好適である。
前記孔を有する基材を製造する方法として、具体的には、少なくとも表面の全部又は一部が金属材料からなる基材の表面に、リチウムイオン源とアルカリ源を含む表面処理剤（
亜鉛イオン及びケイ酸イオンを含むものを除くものであることが好ましい）を接触させる第一工程と、前記表面処理剤を接触させた前記基材の表面上に、無機酸を含む酸性水溶液を接触させる第二工程を含む、製造方法が好適である。
In an embodiment of the present invention, the following chemical etching method is suitable as a method for manufacturing the base material having holes. This chemical etching method is particularly suitable for the production of substrates that have aluminum material on at least all or part of their surface.
Specifically, the method for manufacturing the substrate having pores includes applying a surface treatment agent (containing a lithium ion source and an alkali source) to the surface of a substrate at least in whole or in part made of a metal material.
A first step of contacting the base material (preferably excluding those containing zinc ions and silicate ions) and contacting an acidic aqueous solution containing an inorganic acid on the surface of the base material that has been contacted with the surface treatment agent. Preferably, the manufacturing method includes a second step of
少なくとも表面の全部又は一部が金属材料からなる基材の表面に孔を形成する工程では、少なくとも表面の全部又は一部が金属材料からなる基材の表面に、第一工程の表面処理剤を接触させることにより、リチウム元素を含む皮膜を形成させる。その際、少なくとも表面の全部又は一部が金属材料からなる基材表面の酸化皮膜を含む不動態皮膜の溶解反応を伴う。
リチウム元素を含む皮膜は、公知の方法を用いて形成させることが可能である。例えば、ベーマイト処理や化成処理が挙げられるがこれらに限定されるものではない。ここでリチウム元素を含む皮膜とは、基材由来の金属を含む水酸化皮膜、酸化皮膜、水和酸化皮膜などが含まれる。処理方法としては、例えば、特開昭４８－８９１３８号公報、特開昭５３－１１８４１号公報などに記載の方法を用いることができる。
In the step of forming pores on the surface of a base material at least in whole or in part made of a metal material, the surface treatment agent of the first step is applied to the surface of the base material in which at least all or part of the surface is made of a metal material. By bringing them into contact, a film containing lithium element is formed. At this time, a dissolution reaction of a passive film including an oxide film on the surface of the base material, at least the whole or part of the surface of which is made of a metal material, is involved.
A film containing lithium element can be formed using a known method. Examples include, but are not limited to, boehmite treatment and chemical conversion treatment. Here, the film containing the lithium element includes a hydroxide film, an oxide film, a hydrated oxide film, etc. containing metal derived from the base material. As the treatment method, for example, methods described in Japanese Patent Application Laid-Open No. 48-89138, Japanese Patent Application Laid-Open No. 53-11841, etc. can be used.
第一工程の表面処理剤は、リチウムイオン源及びアルカリ源を成分として含む。 The surface treatment agent in the first step contains a lithium ion source and an alkali source as components.
（リチウムイオン源）
リチウムイオン源の形態は特に限定されず、水酸化物、塩化物、炭酸塩、重炭酸塩、硝酸塩、亜硝酸塩、硫酸塩、過硫酸塩、臭化塩、及び臭素酸塩等から適当なものを１種又は２種以上選択することができる。
本発明の実施形態に係る第一工程に用いる処理液は、リチウムイオンを好ましくは０．００１ｍｏｌ/Ｌ以上５.００ｍｏｌ/Ｌ以下、より好ましくは０．１０ｍｏｌ/Ｌ以上４.
００ｍｏｌ/Ｌ以下、さらに好ましくは０．５０ｍｏｌ/Ｌ以上３.５０ｍｏｌ/Ｌ以下を含む。また、前記リチウム塩濃度は、飽和溶解度を超えていてもよい。
(Lithium ion source)
The form of the lithium ion source is not particularly limited, and may be any suitable one from hydroxide, chloride, carbonate, bicarbonate, nitrate, nitrite, sulfate, persulfate, bromide, bromate, etc. One or more types can be selected.
The treatment liquid used in the first step according to the embodiment of the present invention preferably contains lithium ions in an amount of 0.001 mol/L or more and 5.00 mol/L or less, more preferably 0.10 mol/L or more and 4.0 mol/L or more.
00 mol/L or less, more preferably 0.50 mol/L or more and 3.50 mol/L or less. Further, the lithium salt concentration may exceed the saturated solubility.
（アルカリ源）
第一工程の表面処理剤は、アルカリ源を含む。アルカリ源としては、アルカリ金属又はアルカリ土類金属の水酸物、マグネシウムの水酸化物、又は水溶性アミン化合物を例示できる。
アルカリ金属又はアルカリ土類金属の水酸化物としては、特に限定されず、リチウム、ナトリウム、カリウム、カルシウム等から適当なものを１種又は２種以上選択することができる。
第一工程の表面処理剤は、アルカリ源として、水酸化物イオンを通常０．００１ｍｏｌ/Ｌ以上５.００ｍｏｌ/Ｌ以下、より好ましくは０．００５ｍｏｌ/Ｌ以上４.００ｍｏｌ/Ｌ以下、さらに好ましくは０．０１ｍｏｌ/Ｌ以上３.００ｍｏｌ/Ｌ以下を含む。また、
前記アルカリ金属及び、アルカリ土類金属及びマグネシウムの水酸化物濃度は、飽和溶解度を超えていてもよい。
(alkali source)
The surface treatment agent in the first step contains an alkali source. Examples of the alkali source include alkali metal or alkaline earth metal hydroxides, magnesium hydroxides, and water-soluble amine compounds.
The hydroxide of the alkali metal or alkaline earth metal is not particularly limited, and one or more suitable ones can be selected from lithium, sodium, potassium, calcium, and the like.
The surface treatment agent in the first step contains hydroxide ions as an alkali source, usually in an amount of 0.001 mol/L or more and 5.00 mol/L or less, more preferably 0.005 mol/L or more and 4.00 mol/L or less, and even more preferably includes 0.01 mol/L or more and 3.00 mol/L or less. Also,
The hydroxide concentrations of the alkali metals, alkaline earth metals, and magnesium may exceed their saturation solubility.
水溶性アミン化合物としては、炭素数１～１２のアルキル基が結合した第一級アミン、炭素数１～１２のアルキル基が結合した第二級アミン、炭素数１～１２のアルキル基が結合した第三級アミン、及び炭素数１～１２のヒドロキシアルキル基が結合した第一級アミン、炭素数１～１２のヒドロキシアルキル基が結合した第二級アミン、炭素数１～１２のヒドロキシアルキル基が結合した第三級アミンのいずれもが使用でき、またこれらの水溶性アミンのほかに、前記のアルキル基もしくはヒドロキシアルキル基の一部又は全部がフェノール基で置換された芳香族アミンも用いられる。
また、前記の炭素数１～１２のアルキル基が有する少なくとも１つのメチレンが、－ＮＨ－で置換されていてもよい。
具体的な水溶性アミン化合物は、モノエチルアミン、ジエチルアミン、トリエチルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、ジメチルアミ
ノエタノール、トリエチレンテトラアミン、ヘキサメチレンテトラアミン、エチレンジアミン、及びアンモニア等から適当なものを１種又は２種以上選択することができる。
本発明の実施形態に係る第一工程に用いる処理液は、水溶性アミン化合物を好ましくは０．００１ｍｏｌ/Ｌ以上１.００ｍｏｌ/Ｌ以下、より好ましくは０．００５ｍｏｌ/Ｌ以上０．９０ｍｏｌ/Ｌ以下を挙げることができ、さらに好ましくは、０．０１ｍｏｌ/Ｌ以上０．８０ｍｏｌ/Ｌ以下を含む。
Water-soluble amine compounds include primary amines with an alkyl group of 1 to 12 carbon atoms, secondary amines with an alkyl group of 1 to 12 carbon atoms, and amines with an alkyl group of 1 to 12 carbon atoms. Tertiary amine, primary amine to which a hydroxyalkyl group having 1 to 12 carbon atoms is bonded, secondary amine to which a hydroxyalkyl group having 1 to 12 carbon atoms is bonded, hydroxyalkyl group having 1 to 12 carbon atoms to Any bonded tertiary amine can be used, and in addition to these water-soluble amines, aromatic amines in which part or all of the alkyl or hydroxyalkyl groups mentioned above are substituted with phenol groups can also be used.
Furthermore, at least one methylene of the alkyl group having 1 to 12 carbon atoms may be substituted with -NH-.
Specific water-soluble amine compounds include monoethylamine, diethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, dimethylaminoethanol, triethylenetetraamine, hexamethylenetetraamine, ethylenediamine, and ammonia. One or more types can be selected.
The treatment liquid used in the first step according to the embodiment of the present invention preferably contains a water-soluble amine compound in an amount of 0.001 mol/L or more and 1.00 mol/L or less, more preferably 0.005 mol/L or more and 0.90 mol/L. The following may be mentioned, and more preferably 0.01 mol/L or more and 0.80 mol/L or less.
第一工程の表面処理剤として、アルカリ金属又はアルカリ土類金属の水酸化物、マグネシウムの水酸化物、及び水溶性アミン化合物のうち、一つの成分を単独で用いても、数種類の成分を併用して用いることもできる。 As the surface treatment agent in the first step, one component among alkali metal or alkaline earth metal hydroxides, magnesium hydroxides, and water-soluble amine compounds may be used alone or several components may be used in combination. It can also be used as
第一工程の表面処理剤は、亜鉛イオン及びケイ酸イオンを含まないことが望ましい。亜鉛イオンが存在する場合、金属材料としてアルミニウム材を有する基材を用いる場合、アルミニウム材表面に亜鉛置換皮膜が形成するため所望の孔が得られなくなる。また、ケイ酸イオンが存在する場合、アルミニウム材表面にケイ素を含む皮膜が形成するため所望の孔が得られなくなる。さらに、銅、鉄、ニッケル、錫、などの遷移金属イオンについても含まないことが望ましい。アルカリ金属、及びアルカリ土類金属、及びマグネシウムの水酸化物、これらの塩から供給されるナトリウム、カリウム、マグネシウム、カルシウム等は、皮膜中に含まれてもよい。 It is desirable that the surface treatment agent in the first step does not contain zinc ions and silicate ions. When zinc ions are present, when a base material having an aluminum material is used as the metal material, a zinc substitution film is formed on the surface of the aluminum material, making it impossible to obtain desired pores. Furthermore, when silicate ions are present, a film containing silicon is formed on the surface of the aluminum material, making it impossible to obtain desired pores. Furthermore, it is desirable that transition metal ions such as copper, iron, nickel, and tin are not included. Sodium, potassium, magnesium, calcium, etc. supplied from hydroxides of alkali metals, alkaline earth metals, and magnesium, and salts thereof may be contained in the film.
第一工程の表面処理剤は、リチウムイオン源及びアルカリ源をイオン交換水、工業用水、水道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。前記表面処理剤中には、前記基材及び水由来のアルミニウム、マグネシウム、ケイ素、チタン、クロム、マンガン、鉄、ニッケル、銅、亜鉛等の元素が存在していてもよい。 The surface treatment agent in the first step can be easily prepared by dissolving a lithium ion source and an alkali source in ion-exchanged water, industrial water, tap water, or the like. Elements such as aluminum, magnesium, silicon, titanium, chromium, manganese, iron, nickel, copper, and zinc derived from the base material and water may be present in the surface treatment agent.
第一工程の表面処理剤には、有機溶媒、界面活性剤、キレート剤を添加してもよい。これら他の成分を添加する場合、その合計含有量は、表面処理剤の全量に対して５０.０質
量％以下であることが好ましい。
An organic solvent, a surfactant, and a chelating agent may be added to the surface treatment agent in the first step. When these other components are added, their total content is preferably 50.0% by mass or less based on the total amount of the surface treatment agent.
第一工程の表面処理剤に接触させることによって、少なくとも表面の全部又は一部が金属材料からなる基材表面にリチウム元素を含む皮膜を形成させることができる。前記皮膜の付着量としては、特に制限されず、前記皮膜は連続膜であっても、不連続膜であってもよい。 By bringing it into contact with the surface treatment agent in the first step, a film containing lithium element can be formed on the surface of the base material, at least all or part of which is made of a metal material. The amount of the film deposited is not particularly limited, and the film may be a continuous film or a discontinuous film.
第一工程の表面処理剤を、少なくとも表面の全部又は一部が金属材料からなる基材に接触させる方法としては、浸漬、スプレーによる処理方法が挙げられる。前記表面処理剤を接触させることにより、前記基材上にリチウム元素を含む皮膜を形成させることが可能であるが、電解処理を併用することも可能である。
第一工程で用いるときの表面処理剤の液温は２０.０℃から１００.０℃が好ましい。ｐＨは８.０から１３.０に調整することが好ましい。接触時間は５秒から１８００秒が好ましい。前記第一工程の後は、必要に応じて水洗工程、乾燥工程を行ってもよい。
Examples of the method of bringing the surface treatment agent in the first step into contact with the base material at least in whole or in part of the surface of which is made of a metal material include treatment methods such as dipping and spraying. Although it is possible to form a film containing the lithium element on the base material by bringing the surface treatment agent into contact with the base material, it is also possible to use electrolytic treatment in combination.
The liquid temperature of the surface treatment agent when used in the first step is preferably 20.0°C to 100.0°C. It is preferable to adjust the pH from 8.0 to 13.0. The contact time is preferably from 5 seconds to 1800 seconds. After the first step, a washing step and a drying step may be performed as necessary.
前記第二工程の酸性水溶液は、無機酸を含む。前記無機酸としては、硫酸、硝酸、塩酸、及びアミド硫酸等から適当なものを１種又は２種以上選択することができるが、これらに限定されるものではない。また、前記水溶液には、有機酸、無機酸塩、及び有機酸塩等を含んでもよいが遷移金属を含まないことが望ましい。
前記有機酸としては、蟻酸、クエン酸、シュウ酸、リンゴ酸、コハク酸、マロン酸、エチレンジアミン四酢酸、グルコン酸等から適当なものを１種又は２種以上選択することができるが、これらに限定されるものではない。また、前記無機酸塩及び有機酸塩は、前記無機酸及び有機酸のアルカリ金属塩、アルカリ土類金属塩、アンモニウム塩から適当なも
のを１種又は２種以上選択することができるが、これらに限定されるものではない。前記水溶液は、上記の無機酸、有機酸、又はこれらの塩を１種又は２種類以上配合することができる。前記有機酸、無機酸塩又は有機酸塩いずれか単独の酸性水溶液であっても前記の孔が形成される場合もあるが、工業的な観点から無機酸単独の酸性水溶液が好ましい。
The acidic aqueous solution in the second step contains an inorganic acid. As the inorganic acid, one or more suitable ones can be selected from sulfuric acid, nitric acid, hydrochloric acid, amidosulfuric acid, etc., but the inorganic acid is not limited thereto. Further, the aqueous solution may contain an organic acid, an inorganic acid salt, an organic acid salt, etc., but preferably does not contain a transition metal.
As the organic acid, one or more suitable ones can be selected from formic acid, citric acid, oxalic acid, malic acid, succinic acid, malonic acid, ethylenediaminetetraacetic acid, gluconic acid, etc. It is not limited. The inorganic acid salt and organic acid salt may be selected from one or more appropriate alkali metal salts, alkaline earth metal salts, and ammonium salts of the inorganic acid and organic acid. It is not limited to. The aqueous solution may contain one or more of the above inorganic acids, organic acids, or salts thereof. Although the pores may be formed even if an acidic aqueous solution of any one of the organic acid, an inorganic acid salt, or an organic acid salt is used alone, an acidic aqueous solution of an inorganic acid alone is preferable from an industrial viewpoint.
前記無機酸を含む成分の合計含有量は、酸性水溶液の全量に対して０．１質量％から７０.０質量％であることが好ましく、０．５質量％から５０.０質量％であることがより好ましく、１.０質量％から４５.０質量％であることがさらに好ましい。 The total content of the components containing the inorganic acid is preferably from 0.1% by mass to 70.0% by mass, and from 0.5% by mass to 50.0% by mass based on the total amount of the acidic aqueous solution. is more preferable, and even more preferably from 1.0% by mass to 45.0% by mass.
第二工程の酸性水溶液には、界面活性剤やキレート剤等を添加してもよい。これら他の成分を添加する場合、その合計含有量は、酸性水溶液の全量に対して１０.０質量％以下
であることが好ましい。
A surfactant, a chelating agent, etc. may be added to the acidic aqueous solution in the second step. When adding these other components, the total content thereof is preferably 10.0% by mass or less based on the total amount of the acidic aqueous solution.
第二工程の酸性水溶液は、前記の各成分をイオン交換水、工業用水、水道水等に溶解させることによって容易に調製することができる。前記酸性水溶液中には、前記基材及び水由来のアルミニウム、マグネシウム、ケイ素、チタン、クロム、マンガン、鉄、ニッケル、銅、亜鉛等の元素が存在していてもよい。また、前記第一工程により形成したリチウム元素を含む皮膜の溶解に伴う成分が混入してもよい。 The acidic aqueous solution in the second step can be easily prepared by dissolving each of the above components in ion-exchanged water, industrial water, tap water, or the like. Elements such as aluminum, magnesium, silicon, titanium, chromium, manganese, iron, nickel, copper, and zinc derived from the base material and water may be present in the acidic aqueous solution. Further, components accompanying the melting of the film containing lithium element formed in the first step may be mixed.
第二工程の無機酸を含む酸性水溶液を、少なくとも表面の全部又は一部が金属材料からなる基材に接触させる方法としては、浸漬、スプレーによる処理方法が挙げられる。また、電解処理を併用することも可能である。
第二工程に用いるときの前記酸性水溶液は液温が１０.０℃から８０.０℃が好ましい。ｐＨは酸性であればよく、例えば、ｐＨ６.０以下に調整することが好ましい。接触時間
は１秒から１８００秒程度が好ましく、９００秒以下であることがより好ましい。第二工程の後は、通常、水洗工程や乾燥工程が行われる。水洗工程においては、超音波を併用してもよい。乾燥工程においては、自然乾燥でもよく、ドライヤー、エアーブロー、オーブン等を用いてもよい。
Examples of the method of bringing the acidic aqueous solution containing an inorganic acid into contact with the base material at least in whole or in part on the surface of which is made of a metal material in the second step include treatment methods such as dipping and spraying. Moreover, it is also possible to use electrolytic treatment together.
The acidic aqueous solution used in the second step preferably has a liquid temperature of 10.0°C to 80.0°C. The pH may be acidic, and is preferably adjusted to, for example, pH 6.0 or less. The contact time is preferably about 1 second to 1800 seconds, more preferably 900 seconds or less. After the second step, a washing step and a drying step are usually performed. In the water washing step, ultrasonic waves may be used in combination. In the drying step, natural drying may be used, or a dryer, air blow, oven, etc. may be used.
なお、本発明の実施形態に係る製造方法（孔形成工程）では、金属材料を有する基材の表面を処理する際、金属材料を有する基材の全面を処理してもよく、部分的に処理してもよい。樹脂との優れた接合強度を得るためには樹脂と接合する部位だけを処理すればよい。 In addition, in the manufacturing method (hole forming step) according to the embodiment of the present invention, when treating the surface of the base material having a metal material, the entire surface of the base material having the metal material may be treated, or only a portion of the base material having the metal material may be treated. You may. In order to obtain excellent bonding strength with the resin, it is sufficient to treat only the portion that will be bonded to the resin.
本発明の実施形態に係る孔を有する金属材料を有する基材の製造方法においては、他の工程が存在していてもよい。他の工程の例としては、本発明の実施形態に係る製造方法（孔形成工程）を行う前に、基材が有する金属材料の表面を加工する工程や清浄化させる工程を挙げることができる。また、基材が有する金属材料の表面に孔を形成した後、基材－樹脂硬化物の複合体を製造する方法に供する前に、皮膜を形成する工程を行ってもよい。各工程は、必要であれば繰り返し行ってもよい。以下、各工程を詳述する。 In the method for manufacturing a base material having a metal material having holes according to an embodiment of the present invention, other steps may be present. Examples of other steps include processing and cleaning the surface of the metal material included in the base material before performing the manufacturing method (hole forming step) according to the embodiment of the present invention. Further, after forming the holes on the surface of the metal material of the base material, a step of forming a film may be performed before subjecting the material to the method for producing the base material-cured resin composite. Each step may be repeated if necessary. Each step will be explained in detail below.
（表面加工工程）
本発明の実施形態にかかる基材の製造方法に用いられる、金属材料を有する基材は、本発明の実施形態に係る製造方法（孔形成工程）の前に、ショットブラスト加工、サンドブラスト加工、研削加工等の機械的粗化処理や、レーザー加工、プラズマ加工等の物理的粗化処理や、化学的方法によりあらかじめ粗化処理を実施してもよい。これらの加工後に形成される凹凸形状は問わない。
(Surface processing process)
The base material having a metal material used in the manufacturing method of the base material according to the embodiment of the present invention is subjected to shot blasting, sandblasting, grinding, etc. before the manufacturing method (hole forming step) according to the embodiment of the present invention. The roughening treatment may be performed in advance by mechanical roughening treatment such as machining, physical roughening treatment such as laser processing or plasma processing, or chemical method. The uneven shape formed after these processes does not matter.
（表面清浄工程）
本発明の実施形態にかかる基材の製造方法に用いられる、金属材料を有する基材は、本
発明の実施形態に係る製造方法（孔形成工程）の前に、金属材料の表面を清浄化するため、脱脂処理、酸水溶液による酸処理、及び／又は、アルカリ溶液によるアルカリ処理からなる前処理を行ってもよい。
脱脂処理の方法は、特に限定されず、例えば、溶剤系、水系又はエマルジョン系の脱脂剤を用いることができ、アルカリ塩、界面活性剤等を含んでいてもよい。酸処理による前処理の方法としては、硫酸、硝酸、リン酸、フッ酸等の無機酸や、クエン酸、グルコン酸等の有機酸、これらを混合して調製したものなどを用いることができる。また、アルカリ処理による前処理の方法としては、水酸化ナトリウムや水酸化カリウムなどのアルカリ試薬を調製したもの、又はこれらを混合して調製したものなどを用いることができる。
(Surface cleaning process)
The surface of the metal material used in the method for manufacturing a base material according to the embodiment of the present invention is cleaned before the manufacturing method (pore formation step) according to the embodiment of the present invention. Therefore, a pretreatment consisting of a degreasing treatment, an acid treatment using an aqueous acid solution, and/or an alkali treatment using an alkaline solution may be performed.
The degreasing method is not particularly limited, and for example, a solvent-based, water-based, or emulsion-based degreasing agent may be used, and may contain an alkali salt, a surfactant, and the like. As the pretreatment method by acid treatment, inorganic acids such as sulfuric acid, nitric acid, phosphoric acid, and hydrofluoric acid, organic acids such as citric acid and gluconic acid, and mixtures of these can be used. Further, as a pretreatment method using an alkali treatment, an alkali reagent prepared with an alkali reagent such as sodium hydroxide or potassium hydroxide, or a mixture of these reagents can be used.
（後処理工程）
本発明の実施形態にかかる基材の製造方法（孔形成工程）の実施後、孔を有する金属材料の表面に皮膜を形成させてもよい。皮膜の形成方法は塗布型であっても反応型であってもよく、形成させる皮膜としては、例えば、自然酸化膜、陽極酸化皮膜、化成皮膜（リン酸塩系皮膜、ジルコニウム系皮膜、クロム系皮膜）、シランカップリング剤硬化皮膜、めっき膜等が挙げられるが、これらに限定されない。皮膜を形成する場合、その膜厚は特に限定されないが、１００ｎｍ以下にすることが望ましい。前記皮膜の厚みが１００ｎｍよりも厚い場合、樹脂との接合強度が低下する場合がある。前記皮膜の厚みは、孔の形状に応じて適宜調整することができる。
(Post-processing process)
After implementing the base material manufacturing method (hole forming step) according to the embodiment of the present invention, a film may be formed on the surface of the metal material having holes. The film formation method may be a coating type or a reaction type, and the films to be formed include, for example, natural oxide film, anodic oxide film, chemical conversion film (phosphate-based film, zirconium-based film, chromium-based film, etc.). (film), silane coupling agent cured film, plating film, etc., but are not limited to these. When forming a film, the film thickness is not particularly limited, but is preferably 100 nm or less. If the thickness of the film is thicker than 100 nm, the bonding strength with the resin may decrease. The thickness of the film can be adjusted as appropriate depending on the shape of the pores.
(その他の処理工程)
前述の工程のほか、必要に応じてその他の工程を適宜行ってもよい。例えば、水洗工程はすべての工程（例えば、表面加工工程、表面清浄工程、孔形成工程、後処理工程等）の前後に行ってもよい。また、各水洗工程後に適宜乾燥工程を行ってもよい。
(Other processing steps)
In addition to the above-mentioned steps, other steps may be performed as necessary. For example, the water washing step may be performed before and after all steps (for example, surface processing step, surface cleaning step, hole forming step, post-treatment step, etc.). Further, a drying step may be performed as appropriate after each washing step.
＜基材－樹脂硬化物の複合体の製造方法＞
本発明の実施形態に係る基材－樹脂硬化物の複合体は、基材と樹脂硬化物を含む基材－樹脂複合体であって、該基材が前記で説明した基材であり、該基材が有する金属材料の表面における孔に、樹脂硬化物を含むものである。
本発明の実施形態に係る基材－樹脂硬化物の複合体における樹脂硬化物とは、熱可塑性樹脂、熱硬化性樹脂、熱可塑性エラストマー、樹脂塗料が硬化して塗膜となったもの、接着剤が硬化したものなど、あらゆる樹脂であってよい。
本発明の実施形態に係る基材－樹脂硬化物の複合体の製造方法は、本発明の実施形態に係る基材の製造方法に含まれる工程である孔形成工程と、前記孔形成工程において形成された、金属材料の表面が有する孔に前記樹脂を入れる工程と、を含む。前記孔に前記樹脂を入れる工程の後に、前記樹脂を冷却、放置、又は加熱によって硬化して、基材－樹脂硬化物の複合体を形成する。基材－樹脂硬化物の複合体とは、前記基材と樹脂硬化物のみから構成されるものであってもよいし、前記孔を有する金属材料を有する基材と前記樹脂硬化物に加え、その樹脂硬化物に接触する相手材を含むものであってもよい。前記相手材は、樹脂材料だけでなく、金属、ゴム、木材、セラミック、複合材料を含むあらゆる材料であってよい。また、前記相手材の形状は特に限定されず、板、棒、帯、管、線、フィルム等であってもよい。
<Method for manufacturing base material-cured resin composite>
The substrate-cured resin composite according to the embodiment of the present invention is a substrate-resin composite comprising a substrate and a cured resin, where the substrate is the substrate described above, and The resin cured material is contained in the pores on the surface of the metal material of the base material.
The cured resin in the base material-cured resin composite according to the embodiment of the present invention includes thermoplastic resins, thermosetting resins, thermoplastic elastomers, resin paints that have been cured into a coating film, and adhesives. It may be any type of resin, including one in which the agent has been cured.
The method for producing a substrate-cured resin composite according to the embodiment of the present invention includes a pore forming step, which is a step included in the method for producing a base material according to the embodiment of the present invention; filling the resin into the holes formed in the surface of the metal material. After the step of putting the resin into the holes, the resin is cured by cooling, standing, or heating to form a substrate-cured resin composite. The base material-resin cured product composite may be composed only of the base material and the resin cured product, or may be composed of the base material having the metal material having holes and the resin cured product, It may also include a counterpart material that comes into contact with the cured resin material. The counterpart material may be any material including not only resin material but also metal, rubber, wood, ceramic, and composite material. Furthermore, the shape of the counterpart material is not particularly limited, and may be a plate, rod, band, tube, wire, film, or the like.
本発明の実施形態に係る基材－樹脂硬化物の複合体を製造する具体的な方法としては、孔を有する金属材料を有する基材の表面又は表面上に対して接着剤を塗布した後に相手材を貼り合わせて接合する方法、孔を有する金属材料を有する基材の表面又は表面上に対して樹脂を当て熱圧着により接合する方法、孔を有する金属材料を有する基材の表面又は表面上に対して樹脂を当てレーザー加熱により樹脂を溶融させて金属と樹脂を接合する方法、孔を有する金属材料を有する基材を射出成形用金型内にセットしてこの金型内に溶融した樹脂をインサート成形して接合する方法（以後、射出成形接合と称する）、前記孔を有
する基材の表面又は表面上に対して樹脂塗料を接触させた後に硬化させることで前記基材の表面又は表面上に塗膜を形成する方法などが挙げられる。
A specific method for producing the base material-cured resin composite according to the embodiment of the present invention is to apply an adhesive to the surface of a base material having a metal material having pores or to the surface of the base material, and then A method of joining materials by pasting them together, a method of applying a resin to the surface of a base material having a metal material having holes, or a method of joining by thermocompression bonding, a method of joining the surface of a base material having a metal material having holes or on the surface of the base material having a hole. A method of joining metal and resin by applying a resin to the surface and melting the resin using laser heating. A base material containing a metal material with holes is set in an injection mold, and the resin is melted in the mold. A method of bonding by insert molding (hereinafter referred to as injection molding bonding), a resin coating is brought into contact with the surface or surface of the base material having holes and then cured, thereby bonding the surface or surface of the base material. Examples include a method of forming a coating film thereon.
前記熱可塑性樹脂は、用途に応じて公知の熱可塑性樹脂から選択することができる。例えば、ポリアミド系樹脂、ポリカーボネート系樹脂、ポリビニル系樹脂、ポリフェニレンサルファイド系樹脂、ポリアクリル系樹脂、ポリエステル系樹脂、ポリアセタール系樹脂、アクリロニトリル・ブタジエン・スチレン共重合系樹脂、ポリスチレン系樹脂、ポリイミド系樹脂等から適当なものを１種又は２種以上選択することができるが、これらに限定されるものではない。 The thermoplastic resin can be selected from known thermoplastic resins depending on the purpose. For example, polyamide resin, polycarbonate resin, polyvinyl resin, polyphenylene sulfide resin, polyacrylic resin, polyester resin, polyacetal resin, acrylonitrile-butadiene-styrene copolymer resin, polystyrene resin, polyimide resin, etc. One or more suitable ones can be selected from among the above, but the invention is not limited to these.
前記熱硬化性樹脂は、用途に応じて公知の熱硬化性樹脂から選択することができる。例えば、フェノール樹脂、エポキシ樹脂、ユリア樹脂、メラミン樹脂等から適当なものを１種又は２種以上選択することができるが、これらに限定されるものではない。 The thermosetting resin can be selected from known thermosetting resins depending on the purpose. For example, one or more suitable resins can be selected from phenol resins, epoxy resins, urea resins, melamine resins, etc., but the resin is not limited thereto.
前記熱可塑性エラストマーは、用途に応じて公知の熱可塑性エラストマーから選択することができる。例えば、ポリエステル系エラストマー、塩化ビニル系エラストマー、ポリアミド系エラストマー等から適当なものを１種又は２種以上選択することができるが、これらに限定されるものではない。 The thermoplastic elastomer can be selected from known thermoplastic elastomers depending on the purpose. For example, one or more suitable materials can be selected from polyester elastomers, vinyl chloride elastomers, polyamide elastomers, etc., but the material is not limited thereto.
前記樹脂塗料は、用途に応じて公知の樹脂塗料から選択することができる。例えば、エポキシ系樹脂、アクリル系樹脂、ポリエステル系樹脂、ウレタン系樹脂等から適当なものを１種又は２種以上選択することができるが、これらに限定されるものではない。該塗料は、顔料、分散剤、可塑剤、溶剤などの成分を任意に含んでもよい。 The resin paint can be selected from known resin paints depending on the purpose. For example, one or more suitable resins can be selected from epoxy resins, acrylic resins, polyester resins, urethane resins, etc., but the resin is not limited thereto. The paint may optionally contain components such as pigments, dispersants, plasticizers, and solvents.
前記接着剤は、例えば、塩化ビニル樹脂系接着剤、酢酸ビニル樹脂系接着剤、ポリビニルアルコール系接着剤、ポリアクリル系接着剤、ポリアミド系接着剤、セルロース系接着剤、ユリア樹脂系接着剤、メラミン樹脂系接着剤、フェノール樹脂系接着剤、エポキシ樹脂系接着剤、シリコン樹脂系接着剤、ポリエステル系接着剤、ポリウレタン系接着剤、クロロプレンゴム系接着剤、ニトリルゴム系接着剤、スチレン・ブタジエンゴム系接着剤、シリコンゴム系接着剤、アクリルゴム系接着剤、ウレタンゴム系接着剤、ホットメルト接着剤等から適当なものを１種又は２種以上選択することができるが、これらに限定されるものではない。 Examples of the adhesive include vinyl chloride resin adhesive, vinyl acetate resin adhesive, polyvinyl alcohol adhesive, polyacrylic adhesive, polyamide adhesive, cellulose adhesive, urea resin adhesive, and melamine. Resin adhesives, phenolic resin adhesives, epoxy resin adhesives, silicone resin adhesives, polyester adhesives, polyurethane adhesives, chloroprene rubber adhesives, nitrile rubber adhesives, styrene/butadiene rubber adhesives One or more suitable adhesives can be selected from adhesives, silicone rubber adhesives, acrylic rubber adhesives, urethane rubber adhesives, hot melt adhesives, etc., but are not limited to these. isn't it.
前記、熱可塑性樹脂、熱硬化性樹脂、熱可塑性エラストマー、樹脂塗料、接着剤には公知の充填剤が含まれていてもよい。例えば、ガラス繊維、カーボン繊維、金属繊維、セラミック繊維、ガラスビーズ、カーボン粉末、金属粉末、セラミック粉末、酸化アルミニウム粉末、等から適当なものを１種又は２種以上選択することができるが、これらに限定されるものではない。充填剤の種類、含有量及び形状は、特に限定されるものではない。 The above-mentioned thermoplastic resin, thermosetting resin, thermoplastic elastomer, resin coating, and adhesive may contain a known filler. For example, one or more suitable materials can be selected from glass fiber, carbon fiber, metal fiber, ceramic fiber, glass beads, carbon powder, metal powder, ceramic powder, aluminum oxide powder, etc. It is not limited to. The type, content and shape of the filler are not particularly limited.
本発明の実施形態に係る孔を有する金属材料を有する基材及び樹脂硬化物との複合体の用途
本発明の実施形態に係る孔を有する金属材料を有する基材と、樹脂硬化物との複合体は、自動車用部材、航空機用部材、電子機器用部材、モバイル機器用部材、ＯＡ機器用部材、家電機器用部材、医療機器用部材の材料として有用である。前記孔を有する金属材料を有する基材は、樹脂との接合強度のみならず、めっき膜などの密着性も向上させることができる。なお、本発明の実施形態に係る、孔を有する金属材料を有する基材及び基材－樹脂硬化物の複合体は上記の使用用途に限定されるものではない。
Use of a composite of a base material having a metal material having pores and a cured resin according to an embodiment of the present invention A composite of a base material having a metal material having pores according to an embodiment of the present invention and a cured resin The body is useful as a material for automobile parts, aircraft parts, electronic equipment parts, mobile equipment parts, OA equipment parts, home appliance parts, and medical equipment parts. The base material having the metal material having holes can improve not only the bonding strength with the resin but also the adhesion with the plating film and the like. Note that the base material having a metal material having pores and the base material-cured resin composite according to the embodiments of the present invention are not limited to the above-mentioned uses.
以下に、実施例を比較例とともに挙げ、本発明及びその効果を具体的に説明する。なお
、実施例で使用した基材、すべての処理に用いた薬剤は、市販されている材料や試薬の中から任意に選定したものであり、本発明の実際の用途を限定するものではない。
EXAMPLES Below, the present invention and its effects will be specifically explained using Examples and Comparative Examples. Note that the base materials used in the examples and the chemicals used in all treatments were arbitrarily selected from commercially available materials and reagents, and do not limit the actual use of the present invention.
実施例１から３及び比較例１から３に係る基材－樹脂硬化物の複合体の製造においては、特に断りのない限り、基材として幅２０ｍｍ×長さ４５ｍｍ×厚み１．５ｍｍのアルミニウム材を用いた。 In the production of the substrate-cured resin composites according to Examples 1 to 3 and Comparative Examples 1 to 3, unless otherwise specified, an aluminum material with a width of 20 mm x length of 45 mm x thickness of 1.5 mm was used as the base material. was used.
＜基材－樹脂硬化物の複合体の製造方法＞
実施例１から３及び比較例１から３に係る基材－樹脂硬化物の複合体は、特に断りのない限り、表面清浄工程→孔形成工程(第一工程→第二工程)→射出成形接合工程の各工程を経て製造した。以下、当該処理工程の各処理を説明する。
<Method for manufacturing base material-cured resin composite>
Unless otherwise specified, the substrate-resin cured material composites according to Examples 1 to 3 and Comparative Examples 1 to 3 were prepared by the following steps: surface cleaning step → pore forming step (first step → second step) → injection molding bonding It was manufactured through each step of the process. Each process in the process will be explained below.
（表面清浄工程）
表面清浄工程は、アルカリ脱脂｛ファインクリーナー３１５Ｅ 日本パーカライジング株式会社製、３０ｇ／Ｌ（固形分濃度）、７０℃、浸漬時間１分｝の後、アルカリ洗（水酸化ナトリウム１．０ｍｏｌ／Ｌ、４０℃、浸漬時間１分）を実施し、各工程後に水洗を実施した。
(Surface cleaning process)
The surface cleaning process consisted of alkaline degreasing {Fine Cleaner 315E, manufactured by Nippon Parkerizing Co., Ltd., 30 g/L (solid content concentration), 70°C, immersion time 1 minute}, followed by alkaline washing (sodium hydroxide 1.0 mol/L, 40 ℃, immersion time 1 minute), and washing with water was performed after each step.
（孔形成工程）
第一工程
第一工程は、リチウムイオンを含む表面処理剤に基材を浸漬した後、水洗を実施した。ｐＨに関しては、硝酸水溶液及び水酸化ナトリウム水溶液を用いて調整した。
(pore formation process)
First Step In the first step, the base material was immersed in a surface treatment agent containing lithium ions, and then washed with water. The pH was adjusted using a nitric acid aqueous solution and a sodium hydroxide aqueous solution.
第二工程
第二工程は、無機酸を含む酸性水溶液に基材を浸漬した後、水洗及び乾燥を実施した。
Second Step In the second step, the base material was immersed in an acidic aqueous solution containing an inorganic acid, and then washed with water and dried.
（射出成形接合工程）
射出成形接合工程は、前記孔形成工程後の基材に対し、ガラスファイバーを３０％含むポリフェニレンサルファイド樹脂（ＰＰＳ樹脂）を射出成形した。射出成形には東洋機械金属株式会社製電動サーボ射出成形機（Ｓｉ－５０ＩＩＩ）を用いた。射出成形条件は、プレヒート１２５℃、成形温度３２０℃、金型温度１３５℃、射出速度３０ｍｍ／秒、射出圧力１０００ｋｇｆ、保圧１２００ｋｇｆ、冷却時間１５秒とした。成形されたＰＰＳ樹脂の寸法は、幅１０ｍｍ×長さ４５ｍｍ×厚み３ｍｍである。また、基材とＰＰＳ樹脂の接合面積は１０ｍｍ×５ｍｍである。
(Injection molding joining process)
In the injection molding bonding step, polyphenylene sulfide resin (PPS resin) containing 30% glass fiber was injection molded onto the base material after the hole forming step. For injection molding, an electric servo injection molding machine (Si-50III) manufactured by Toyo Kikai Kinzoku Co., Ltd. was used. The injection molding conditions were preheating at 125° C., molding temperature at 320° C., mold temperature at 135° C., injection speed at 30 mm/sec, injection pressure at 1000 kgf, holding pressure at 1200 kgf, and cooling time at 15 seconds. The dimensions of the molded PPS resin are 10 mm width x 45 mm length x 3 mm thickness. Further, the bonding area between the base material and the PPS resin is 10 mm x 5 mm.
以下、上述した基材及び処理工程に基づき、実施例１から３及び比較例１から３に係る基材－樹脂硬化物の複合体を製造した。以下に、実施例及び比較例での手順等を述べる。 Hereinafter, base material-cured resin composites according to Examples 1 to 3 and Comparative Examples 1 to 3 were manufactured based on the base materials and treatment steps described above. Below, procedures etc. in Examples and Comparative Examples will be described.
［実施例１］
基材として、ＪＩＳ Ｈ ４０００で規格されたＡ２０１７を用いた。第一工程として、以下の処理液（１）を用いて基材を３００秒間浸漬した。第二工程として、以下の処理液（２）を用いて、基材を１８０秒間浸漬した。このようにして、実施例１に係る基材－樹脂硬化物の複合体を得た。
[Example 1]
A2017 standardized by JIS H 4000 was used as the base material. As a first step, the substrate was immersed for 300 seconds using the following treatment liquid (1). As a second step, the substrate was immersed for 180 seconds using the following treatment liquid (2). In this way, a substrate-cured resin composite according to Example 1 was obtained.
処理液（１）は、目的の容量で、３．０ｍｏｌ／Ｌ（モル／Ｌ）となる塩化リチウムと、０．１ｍｏｌ／Ｌとなる硝酸マグネシウム６水和物と、をイオン交換水に加え、ハンディｐＨメーター（東亜ディーケーケー株式会社製ポータブルｐＨ計ＨＭ－３０Ｐ）とｐＨ計測用電極（同社製ＧＳＴ－２７３９Ｃ）でｐＨを計測しながら、硝酸と水酸化ナトリウムを用いて、それをｐＨ１０．０に調整し、目標の容量に調整した。処理液（１）の温度は６０℃とした。 The treatment liquid (1) is prepared by adding 3.0 mol/L (mol/L) of lithium chloride and 0.1 mol/L (0.1 mol/L) of magnesium nitrate hexahydrate to ion-exchanged water. While measuring the pH with a handy pH meter (portable pH meter HM-30P manufactured by Toa DKK Co., Ltd.) and a pH measurement electrode (GST-2739C manufactured by the same company), adjust the pH to 10.0 using nitric acid and sodium hydroxide. Adjustments were made to the target capacity. The temperature of the treatment liquid (1) was 60°C.
処理液（２）は、イオン交換水に対して、硝酸が６．５ｍｏｌ／Ｌ（モル／Ｌ）となるように加えた。今回の例示では、ｐＨ調整は実施しなかった。処理液（２）の温度は５０℃とした。 The treatment liquid (2) was added to ion-exchanged water so that nitric acid was 6.5 mol/L (mol/L). In this example, pH adjustment was not performed. The temperature of the treatment liquid (2) was 50°C.
［実施例２］
基材をＪＩＳ Ｈ４０００で規格されたＡ３００３に変更した点以外は［実施例１］と
同様の方法で［実施例２］の基材－樹脂硬化物の複合体を製造した。
[Example 2]
A base material-cured resin composite of [Example 2] was produced in the same manner as [Example 1] except that the base material was changed to A3003 specified by JIS H4000.
［実施例３］
基材をＪＩＳ Ｈ４０００で規格されたＡ５０５２に変更した点以外は［実施例１］と
同様の方法で［実施例３］の基材－樹脂硬化物の複合体を製造した。
[Example 3]
A base material-cured resin composite of [Example 3] was produced in the same manner as [Example 1] except that the base material was changed to A5052 specified by JIS H4000.
［比較例１］
基材をＪＩＳ Ｈ４０００で規格されたＡ２０１７とした。第一工程及び第二工程の処
理条件を変更した点以外は［実施例１］と同様の方法で、基材－樹脂硬化物の複合体を製造した。具体的には、第一工程として、以下の処理液（３）を用いて基材を６０秒間浸漬した。第二工程として、以下の処理液（４）を用いて、基材を３００秒間浸漬した。
[Comparative example 1]
The base material was A2017 standardized by JIS H4000. A base material-cured resin composite was produced in the same manner as in [Example 1] except that the processing conditions of the first and second steps were changed. Specifically, as the first step, the substrate was immersed for 60 seconds in the following treatment liquid (3). As a second step, the substrate was immersed for 300 seconds using the following treatment liquid (4).
処理液（３）は、目的の容量で、４．２０ｍｏｌ／Ｌ（モル／Ｌ）となる水酸化ナトリウムと、０．６６ｍｏｌ／Ｌとなる硝酸亜鉛と、０．０６ｍｏｌ／Ｌとなるチオ硫酸ナトリウムと、をイオン交換水に加え、目標の容量に調整した。処理液（３）の温度は３５℃とした。 The treatment liquid (3) has a target volume of sodium hydroxide of 4.20 mol/L (mol/L), zinc nitrate of 0.66 mol/L, and sodium thiosulfate of 0.06 mol/L. and were added to ion-exchanged water and adjusted to the target volume. The temperature of the treatment liquid (3) was 35°C.
処理液（４）は、目的の容量で、０．８４ｍｏｌ／Ｌ（モル／Ｌ）となる硫酸と、０．９６ｍｏｌ／Ｌとなる塩化第二鉄と、０．０３ｍｏｌ／Ｌとなる塩化第二銅と、０．０５ｍｏｌ／Ｌとなる硫酸マンガン１水和物と、をイオン交換水に加えた。今回の例示では、ｐＨ調整は実施しなかった。処理液（４）の温度は３０℃とした。 The treatment liquid (4) has a target volume of sulfuric acid of 0.84 mol/L (mol/L), ferric chloride of 0.96 mol/L, and ferric chloride of 0.03 mol/L. Copper and manganese sulfate monohydrate at a concentration of 0.05 mol/L were added to ion exchange water. In this example, pH adjustment was not performed. The temperature of the treatment liquid (4) was 30°C.
［比較例２］
基材をＪＩＳ Ｈ４０００で規格されたＡ３００３に変更した点以外は［比較例１］と
同様の方法で［比較例２］の基材－樹脂硬化物の複合体を製造した。
[Comparative example 2]
A composite of the base material and cured resin of [Comparative Example 2] was produced in the same manner as [Comparative Example 1] except that the base material was changed to A3003 specified by JIS H4000.
［比較例３］
基材をＪＩＳ Ｈ４０００で規格されたＡ５０５２に変更した点以外は［比較例１］と
同様の方法で［比較例３］の基材－樹脂硬化物の複合体を製造した。
[Comparative example 3]
A base material-cured resin composite of [Comparative Example 3] was produced in the same manner as [Comparative Example 1] except that the base material was changed to A5052 specified by JIS H4000.
（断面曲線の負荷長さ率）
実施例１から３及び比較例１から３の処理後の基材の断面曲線の負荷長さ率の測定は、前記処理後の基材を電界放出形走査電子顕微鏡（日立ハイテクノロジーズ製、Ｓ－４７００ＴｙｐｅＩＩ）により、倍率１万倍で断面観察を行い、得られた断面観察写真について画像処理ソフト（ＩｍａｇｅＪ）を用いて測定した。切断レベル３０％、評価長さ１０μｍにおける断面曲線の負荷長さ率が４０％以上の場合を良（「○」）とし、４０％未満及び算出不可能な場合を悪（「×」）とした。結果を表１に示す。
(Load length ratio of cross-sectional curve)
Measurement of the load length ratio of the cross-sectional curve of the substrate after treatment in Examples 1 to 3 and Comparative Examples 1 to 3 was carried out using a field emission scanning electron microscope (manufactured by Hitachi High Technologies, S- 4700 Type II) at a magnification of 10,000 times, and the obtained cross-sectional observation photographs were measured using image processing software (ImageJ). When the load length ratio of the cross-sectional curve at a cutting level of 30% and an evaluation length of 10 μm is 40% or more, it is marked as good ("○"), and when it is less than 40% or cannot be calculated, it is marked as bad ("x"). . The results are shown in Table 1.
（アスペクト比）
アスペクト比は、孔の入口における直径の平均値（ａ）と、孔深さの平均値（ｂ）の比（ｂ／ａ）により算出した。
孔の入口における直径の平均値（ａ）は、実施例１から３及び比較例１から３の処理後の基材の表面を前記電子顕微鏡により、倍率５万倍で撮影した写真から測定した。孔の開
口部の直径又は短径の長いものから上位１０個を選択し、それらの長さを測定し、全てを積算して１０で除したものを孔の入口における直径の平均値とした。
孔深さの平均値（ｂ）は、実施例１から３及び比較例１から３の処理後の基材の断面を前記電子顕微鏡により、倍率３万倍で撮影した写真から測定した。孔深さの長いものから上位１０個を選択し、それらの最上部から最深部の長さを測定し、全てを積算して１０で除したものを孔深さの平均値とした。
アスペクト比（ｂ／ａ）が２以上の場合を良（「○」）、２未満及び算出不可能な場合を悪（「×」）とした。結果を表１に示す。
(aspect ratio)
The aspect ratio was calculated from the ratio (b/a) of the average value of the diameter at the entrance of the hole (a) to the average value of the hole depth (b).
The average value (a) of the diameter at the entrance of the pores was measured from photographs taken at a magnification of 50,000 times using the electron microscope described above of the surfaces of the substrates after treatment in Examples 1 to 3 and Comparative Examples 1 to 3. The top 10 hole openings with the longest diameter or short axis were selected, their lengths were measured, and all the lengths were integrated and divided by 10, which was taken as the average value of the diameter at the hole entrance.
The average value (b) of the pore depth was measured from photographs of cross sections of the treated substrates of Examples 1 to 3 and Comparative Examples 1 to 3 taken at a magnification of 30,000 times using the electron microscope. The top 10 holes were selected from those with the longest hole depths, the lengths from the top to the deepest part were measured, and all the lengths were integrated and divided by 10 to determine the average value of the hole depths.
A case where the aspect ratio (b/a) was 2 or more was judged as good ("○"), and a case where the aspect ratio (b/a) was less than 2 or could not be calculated was judged as bad ("x"). The results are shown in Table 1.
（引張せん断試験）
実施例１から３及び比較例１から３の基材－樹脂硬化物の複合体について、ＩＳＯ１９０９５－３に規格化された引張せん断試験方法により接合強度を評価した。引張せん断試験は、株式会社島津製作所製オートグラフ精密万能試験機（ＡＧ－１００ｋＮＸ）を使用した。評価は、室温２５℃、引張速度１０ｍｍ／分の条件にて行った。引張せん断強度（接合強度：ＭＰａ）は破壊荷重（Ｎ）／接合部面積（５０ｍｍ２）として算出した。引張せん断試験後の基材と樹脂硬化物との間の接合部の破壊形態を目視で調べた。
結果を表１に示す。樹脂硬化物が基材側の接合面積に対して７０％以上の面積に残存する破壊形態である場合を良（「〇」）、樹脂硬化物が基材側の接合面積に対して１０％以上７０％未満の面積に残存する破壊形態である場合を悪（「×」）、樹脂硬化物が基材側の接合面積に対して１０％未満の面積に残存する破壊形態である場合をさらに悪（「××」）とした。接合強度が３０ＭＰａ以上で、接合部の破壊形態の評価が良（「○」）の場合、樹脂との接合強度が優れていると定義した。
(Tensile shear test)
The bonding strength of the base material-cured resin composites of Examples 1 to 3 and Comparative Examples 1 to 3 was evaluated using a tensile shear test method standardized in ISO 19095-3. For the tensile shear test, an Autograph Precision Universal Testing Machine (AG-100kNX) manufactured by Shimadzu Corporation was used. The evaluation was performed at a room temperature of 25° C. and a tensile speed of 10 mm/min. The tensile shear strength (joint strength: MPa) was calculated as breaking load (N)/joint area (50 mm 2 ). After the tensile shear test, the fracture form of the joint between the base material and the cured resin was visually examined.
The results are shown in Table 1. Good ("〇") if the cured resin material remains in a fracture form that is 70% or more of the bonded area on the base material side, and the cured resin material is 10% or more of the bonded area on the base material side. A case where the fracture form remains in less than 70% of the area is considered bad (“x”), and a case where the fracture form remains in an area of less than 10% of the bonded area of the resin cured product on the base material side is considered worse. (“XX”). When the bonding strength was 30 MPa or more and the evaluation of the fracture form of the bonded portion was good (“◯”), it was defined that the bonding strength with the resin was excellent.
Claims (2)
（１）断面曲線の負荷長さ率(Ｐｍｒ)が切断レベル３０％、評価長さ１０μｍにおいて４０％以上である
（２）孔の入口における直径の平均値（ａ）と、孔深さの平均値（ｂ）とのアスペクト比（ｂ／ａ）が２以上５０以下である A base material at least in whole or in part made of a metal material, the surface of the metal material has pores, and satisfies the following requirements (1) and (2).
(1) The load length ratio (Pmr) of the cross-sectional curve is 40% or more at the cutting level of 30% and the evaluation length of 10 μm. (2) The average value of the diameter at the entrance of the hole (a) and the average of the hole depth The aspect ratio (b/a) to the value (b) is 2 or more and 50 or less
A base material-resin composite comprising a base material and a cured resin material, wherein the base material is the base material according to claim 1, and the cured resin material is filled in the pores on the surface of the metal material of the base material. A composite of a base material and a cured resin.
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| WO2007114261A1 (en) | 2006-03-31 | 2007-10-11 | Kabushiki Kaisha Kobe Seiko Sho | High-strength cold rolled steel sheet excelling in chemical treatability |
| JP2008189914A (en) | 2007-01-10 | 2008-08-21 | Mitsubishi Rayon Co Ltd | Formed body and method for manufacturing the same |
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| JP2017019164A (en) | 2015-07-09 | 2017-01-26 | 三井化学株式会社 | Metal/resin composite structure and method for manufacturing metal/resin composite structure |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2007114261A1 (en) | 2006-03-31 | 2007-10-11 | Kabushiki Kaisha Kobe Seiko Sho | High-strength cold rolled steel sheet excelling in chemical treatability |
| JP2008189914A (en) | 2007-01-10 | 2008-08-21 | Mitsubishi Rayon Co Ltd | Formed body and method for manufacturing the same |
| JP2010137475A (en) | 2008-12-12 | 2010-06-24 | Furukawa-Sky Aluminum Corp | Resin-coated aluminum sheet with excellent resin adhesiveness |
| JP2016142119A (en) | 2015-02-05 | 2016-08-08 | 三井化学株式会社 | Arm for door checker and door checker |
| JP2017019164A (en) | 2015-07-09 | 2017-01-26 | 三井化学株式会社 | Metal/resin composite structure and method for manufacturing metal/resin composite structure |
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