TW202341827A - Structural body, method for manufacturing structural body, and composite body - Google Patents
Structural body, method for manufacturing structural body, and composite body Download PDFInfo
- Publication number
- TW202341827A TW202341827A TW112102958A TW112102958A TW202341827A TW 202341827 A TW202341827 A TW 202341827A TW 112102958 A TW112102958 A TW 112102958A TW 112102958 A TW112102958 A TW 112102958A TW 202341827 A TW202341827 A TW 202341827A
- Authority
- TW
- Taiwan
- Prior art keywords
- plating layer
- porous structure
- pores
- layer
- base material
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000002131 composite material Substances 0.000 title 1
- 238000007747 plating Methods 0.000 claims abstract description 97
- 239000011148 porous material Substances 0.000 claims abstract description 80
- 239000000463 material Substances 0.000 claims abstract description 50
- 229910052743 krypton Inorganic materials 0.000 claims abstract description 7
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001179 sorption measurement Methods 0.000 claims abstract description 7
- 229920005989 resin Polymers 0.000 claims description 46
- 239000011347 resin Substances 0.000 claims description 46
- 238000005530 etching Methods 0.000 claims description 29
- 238000009713 electroplating Methods 0.000 claims description 24
- 230000000844 anti-bacterial effect Effects 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- 150000007522 mineralic acids Chemical class 0.000 claims description 8
- 239000007800 oxidant agent Substances 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 72
- 229910052759 nickel Inorganic materials 0.000 description 36
- 238000012360 testing method Methods 0.000 description 25
- 239000000243 solution Substances 0.000 description 23
- 229910052782 aluminium Inorganic materials 0.000 description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 19
- 241000894006 Bacteria Species 0.000 description 17
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- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- -1 trioctylmethane Chemical compound 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
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- 238000011156 evaluation Methods 0.000 description 7
- 239000004743 Polypropylene Substances 0.000 description 6
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- 230000009849 deactivation Effects 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 6
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 125000001165 hydrophobic group Chemical group 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 5
- 230000001580 bacterial effect Effects 0.000 description 4
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- 125000002091 cationic group Chemical group 0.000 description 3
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- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 229920006048 Arlen™ Polymers 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 241000134304 Influenza A virus H3N2 Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000004697 Polyetherimide Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004954 Polyphthalamide Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000000840 anti-viral effect Effects 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
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- 239000003795 chemical substances by application Substances 0.000 description 2
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- 238000010411 cooking Methods 0.000 description 2
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- 239000000806 elastomer Substances 0.000 description 2
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- 208000015181 infectious disease Diseases 0.000 description 2
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- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001230 polyarylate Polymers 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 229920001601 polyetherimide Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
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- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
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- 229910052718 tin Inorganic materials 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- NDZFNTHGIIQMQI-UHFFFAOYSA-N 1-benzylpyridin-1-ium Chemical compound C=1C=CC=C[N+]=1CC1=CC=CC=C1 NDZFNTHGIIQMQI-UHFFFAOYSA-N 0.000 description 1
- VUQPJRPDRDVQMN-UHFFFAOYSA-N 1-chlorooctadecane Chemical class CCCCCCCCCCCCCCCCCCCl VUQPJRPDRDVQMN-UHFFFAOYSA-N 0.000 description 1
- FFYRIXSGFSWFAQ-UHFFFAOYSA-N 1-dodecylpyridin-1-ium Chemical compound CCCCCCCCCCCC[N+]1=CC=CC=C1 FFYRIXSGFSWFAQ-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- JGFDZZLUDWMUQH-UHFFFAOYSA-N Didecyldimethylammonium Chemical compound CCCCCCCCCC[N+](C)(C)CCCCCCCCCC JGFDZZLUDWMUQH-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
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- 229930182556 Polyacetal Natural products 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 230000002155 anti-virotic effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 1
- CYDRXTMLKJDRQH-UHFFFAOYSA-N benzododecinium Chemical compound CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 CYDRXTMLKJDRQH-UHFFFAOYSA-N 0.000 description 1
- QSRFYFHZPSGRQX-UHFFFAOYSA-N benzyl(tributyl)azanium Chemical compound CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 QSRFYFHZPSGRQX-UHFFFAOYSA-N 0.000 description 1
- VBQDSLGFSUGBBE-UHFFFAOYSA-N benzyl(triethyl)azanium Chemical compound CC[N+](CC)(CC)CC1=CC=CC=C1 VBQDSLGFSUGBBE-UHFFFAOYSA-N 0.000 description 1
- YOUGRGFIHBUKRS-UHFFFAOYSA-N benzyl(trimethyl)azanium Chemical compound C[N+](C)(C)CC1=CC=CC=C1 YOUGRGFIHBUKRS-UHFFFAOYSA-N 0.000 description 1
- WNBGYVXHFTYOBY-UHFFFAOYSA-N benzyl-dimethyl-tetradecylazanium Chemical compound CCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 WNBGYVXHFTYOBY-UHFFFAOYSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 239000005548 dental material Substances 0.000 description 1
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 1
- 229940078672 didecyldimethylammonium Drugs 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- VICYBMUVWHJEFT-UHFFFAOYSA-N dodecyltrimethylammonium ion Chemical compound CCCCCCCCCCCC[N+](C)(C)C VICYBMUVWHJEFT-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000003703 image analysis method Methods 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 229940127554 medical product Drugs 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- AICMYQIGFPHNCY-UHFFFAOYSA-J methanesulfonate;tin(4+) Chemical compound [Sn+4].CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O AICMYQIGFPHNCY-UHFFFAOYSA-J 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- CLNYHERYALISIR-UHFFFAOYSA-N nona-1,3-diene Chemical compound CCCCCC=CC=C CLNYHERYALISIR-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 229940127557 pharmaceutical product Drugs 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- PDSVZUAJOIQXRK-UHFFFAOYSA-N trimethyl(octadecyl)azanium Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)C PDSVZUAJOIQXRK-UHFFFAOYSA-N 0.000 description 1
- GLFDLEXFOHUASB-UHFFFAOYSA-N trimethyl(tetradecyl)azanium Chemical compound CCCCCCCCCCCCCC[N+](C)(C)C GLFDLEXFOHUASB-UHFFFAOYSA-N 0.000 description 1
- ZNEOHLHCKGUAEB-UHFFFAOYSA-N trimethylphenylammonium Chemical compound C[N+](C)(C)C1=CC=CC=C1 ZNEOHLHCKGUAEB-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/16—Electroplating with layers of varying thickness
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
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Abstract
Description
本發明係關於構造體、構造體之製造方法及接合體。The present invention relates to a structure, a manufacturing method of the structure, and a joint body.
將金屬構件的表面粗化之方法，被提案有：對金屬構件的表面施行蝕刻而形成微米等級的凹凸構造(基底粗面)，再對基底粗面的表面進一步施行蝕刻而形成樹枝狀層(精細粗面)的方法(例如參照專利文獻1)。 [先前技術文獻] [專利文獻] A method for roughening the surface of a metal member has been proposed: etching the surface of the metal member to form a micron-level uneven structure (base roughening), and then further etching the base roughening surface to form a dendritic layer ( fine rough surface) method (for example, refer to Patent Document 1). [Prior technical literature] [Patent Document]
[專利文獻1]國際公開第2020/158820號[Patent Document 1] International Publication No. 2020/158820
(發明所欲解決之問題)(The problem that the invention wants to solve)
利用專利文獻1所記載方法對表面施行粗化的金屬構件，係藉由具有微米等級的基底粗面、與在其表面所形成的精細粗面，例如可對樹脂構件發揮優異的接合強度。另一方面，依照金屬構件的材質，會有利用專利文獻1所記載方法並無法形成良好凹凸構造的情形。The metal member whose surface is roughened by the method described in Patent Document 1 can exhibit excellent bonding strength to, for example, a resin member by having a micron-level base rough surface and a fine rough surface formed on the surface. On the other hand, depending on the material of the metal member, the method described in Patent Document 1 may not be able to form a good uneven structure.
例如，製造壓鑄(鑄造品)時所使用的鋁合金，係為了提高成形時的流動性而大量含有矽。若對此種鋁合金利用專利文獻1所記載的方法實施粗化處理，則有對蝕刻液欠缺溶解性的矽於經粗化處理的面析出而無法獲得充分接合強度的情形。For example, aluminum alloys used in the production of die-cast products contain a large amount of silicon in order to improve fluidity during molding. If such an aluminum alloy is roughened by the method described in Patent Document 1, silicon lacking solubility in the etching liquid may precipitate on the roughened surface, and sufficient joint strength may not be obtained.
有鑑於上述實情，本發明之一實施形態的課題在於提供，無論基材的材質如何，均可於表面形成具有微細凹凸構造的構造體及其製造方法、以及含有該構造體的接合體。 (解決問題之技術手段) In view of the above, an object of one embodiment of the present invention is to provide a structure that can form a fine uneven structure on the surface regardless of the material of the base material, a manufacturing method thereof, and a joint body including the structure. (Technical means to solve problems)
用於解決上述課題的手段係包括以下實施態樣。 ＜1＞一種構造體，係具有：基材、與配置於上述基材上的電鍍層； 上述電鍍層係在與上述基材的相反側表面設有多孔質構造，且滿足下述(1)~(3)中之至少一項： (1)多孔質構造係具有：第1細孔、與在第1細孔表面所形成的第2細孔； (2)電鍍層設有多孔質構造的表面之突出谷部深度(Rvk)為0.3μm以上； (3)電鍍層設有多孔質構造的表面，利用氪吸附法所測定實際表面積(m 2)除以幾何表面積(m 2)所獲得的粗糙度指數為12以上。 ＜2＞如＜1＞所記載的構造體，係滿足上述(1)。 ＜3＞如＜1＞所記載的構造體，係滿足上述(2)。 ＜4＞如＜1＞所記載的構造體，係滿足上述(3)。 ＜5＞如＜1＞~＜4＞中任一項所記載的構造體，其中，上述電鍍層係含有2層以上的電鍍層。 ＜6＞如＜1＞~＜4＞中任一項所記載的構造體，係使用作為抗菌構件。 ＜7＞一種接合體，係具有：＜1＞~＜4＞中任一項所記載的構造體、與於上述構造體形成有上述電鍍層之面接合的樹脂構件。 ＜8＞一種構造體之製造方法，係包括有： 在基材上形成具多孔質構造之電鍍層的步驟；以及 使上述電鍍層的表面與蝕刻液接觸的步驟。 ＜9＞如＜8＞所記載的構造體之製造方法，其中，上述蝕刻液係含有氧化劑與無機酸。 (對照先前技術之功效) Means for solving the above problems include the following embodiments. <1> A structure having a base material and a plating layer disposed on the base material; the plating layer has a porous structure on the surface opposite to the base material and satisfies the following (1) ~At least one of (3): (1) The porous structure has: a first pore and a second pore formed on the surface of the first pore; (2) The plating layer is provided with a porous structure The protruding valley depth (Rvk) of the surface is 0.3μm or more; (3) The electroplated layer has a porous structure on the surface, and the actual surface area (m 2 ) measured by the krypton adsorption method is divided by the geometric surface area (m 2 ). The roughness index is 12 or above. <2> The structure described in <1> satisfies the above (1). <3> The structure described in <1> satisfies the above (2). <4> The structure described in <1> satisfies the above (3). <5> The structure according to any one of <1> to <4>, wherein the electroplated layer contains two or more electroplated layers. <6> The structure according to any one of <1> to <4> is used as an antibacterial member. <7> A joint body comprising: the structure according to any one of <1> to <4>, and a resin member bonded to a surface of the structure on which the plating layer is formed. <8> A method of manufacturing a structure, which includes: forming a plating layer with a porous structure on a base material; and bringing the surface of the plating layer into contact with an etching liquid. <9> The method for manufacturing a structure according to <8>, wherein the etching liquid contains an oxidizing agent and an inorganic acid. (Compare the effectiveness of previous technologies)
根據本發明一實施形態，可提供：無論基材的材質如何均於表面具有微細凹凸構造的構造體及其製造方法、以及含有該構造體的接合體。According to one embodiment of the present invention, it is possible to provide a structure having a fine uneven structure on its surface regardless of the material of the base material, a manufacturing method thereof, and a joint body including the structure.
本發明中，使用「~」所表示的數值範圍，係表示包含分別以「~」前後所記載數值為最小值與最大值的範圍。 在本發明中階段性所記載的數值範圍中，某數值範圍所記載的上限值或下限值，亦可被置換為其他階段性所記載的數值範圍的上限值或下限值，又，亦可被置換為實施例所示的值。 在本發明中，材料中各成分的量當有符合材料中各成分的物質具有複數個存在之情形時，在未特別聲明之前提下，意指材料中所存在複數個物質的合計量。 In the present invention, the numerical range represented by "~" means the range including the minimum value and the maximum value of the numerical values written before and after "~" respectively. Among the numerical ranges described in stages in the present invention, the upper limit or lower limit described in a certain numerical range can also be replaced by the upper limit or lower limit of the numerical range described in other stages. , can also be replaced with the value shown in the embodiment. In the present invention, when there are multiple substances corresponding to each component in the material, the amount of each component in the material means the total amount of the plurality of substances present in the material unless otherwise stated.
＜構造體＞ 本發明的構造體係具有：基材、與配置於上述基材上的電鍍層； 上述電鍍層係在與上述基材的相反側表面設有多孔質構造，且滿足下述(1)~(3)中之至少一項： (1)多孔質構造係具有：第1細孔、與在第1細孔表面所形成的第2細孔； (2)電鍍層設有多孔質構造的表面之突出谷部深度(Rvk)為0.3μm以上； (3)電鍍層設有多孔質構造的表面，利用氪吸附法所測定實際表面積(m 2)除以幾何表面積(m 2)所獲得的粗糙度指數為12以上。 <Structure> The structural system of the present invention includes a base material and a plating layer disposed on the base material; the plating layer has a porous structure on the surface opposite to the base material and satisfies the following (1) )~(3) at least one: (1) The porous structure has: a first pore and a second pore formed on the surface of the first pore; (2) The electroplated layer is provided with a porous structure The protruding valley depth (Rvk) of the surface is more than 0.3μm; (3) The electroplated layer has a porous structure on the surface, and the actual surface area (m 2 ) measured by the krypton adsorption method is divided by the geometric surface area (m 2 ). The roughness index is 12 or above.
本實施形態的構造體係配置於基材上的電鍍層，在與基材的相反側表面設有多孔質構造，且滿足(1)~(3)中之至少一項。亦即，在構造體表面形成微細的凹凸構造。所以，例如當構造體與其他構件接合時，可充分確保構造體與其他構件所接觸部分的微觀面積，並達成優異的接合強度。 又，本發明的構造體中，可取代基材而使被配置於基材上的電鍍層具有多孔質構造。所以，基材的材質並不被侷限於可形成多孔質構造者。 The electroplating layer of the structural system of this embodiment arranged on the base material has a porous structure on the surface opposite to the base material, and satisfies at least one of (1) to (3). That is, a fine uneven structure is formed on the surface of the structure. Therefore, for example, when the structure is joined to other members, the microscopic area of the contact portion between the structure and other members can be sufficiently ensured, and excellent joint strength can be achieved. Furthermore, in the structure of the present invention, the plating layer disposed on the base material may have a porous structure instead of the base material. Therefore, the material of the base material is not limited to one that can form a porous structure.
(基材) 構造體的基材材質並無特別的限制，可從金屬、樹脂、陶瓷、玻璃、木材等之中選擇。 基材可具有導電性、亦可不具有導電性。當基材不具有導電性的情形時，對基材表面賦予導電性的層亦可被配置於基材與電鍍層之間。 (Substrate) The base material of the structure is not particularly limited and can be selected from metal, resin, ceramics, glass, wood, etc. The base material may or may not be electrically conductive. When the base material does not have conductivity, a layer that imparts conductivity to the surface of the base material may be disposed between the base material and the plating layer.
當基材係含有金屬的情形時，金屬具體而言可舉例如：從鐵、銅、鎳、金、銀、白金、鈷、鋅、鉛、錫、鈦、鉻、鋁、鎂及錳中選擇的金屬；以及含有從上述金屬中選擇之至少1種的合金。When the base material contains a metal, specific examples of the metal include iron, copper, nickel, gold, silver, platinum, cobalt, zinc, lead, tin, titanium, chromium, aluminum, magnesium, and manganese. metal; and an alloy containing at least one selected from the above metals.
當基材含有樹脂的情形時，樹脂亦可從後述含有樹脂構件的樹脂中選擇。When the base material contains resin, the resin may be selected from resins containing resin members described later.
(電鍍層) 被配置於基材上的電鍍層係在與基材的相反側表面設有多孔質構造。 (Electroplating layer) The plating layer arranged on the base material has a porous structure on the surface opposite to the base material.
本發明中所謂「多孔質構造」係意指觀察電鍍層沿厚度方向切斷所獲得的截面時存在的細孔，且截面每10μm觀察到的細孔數之平均值為5個以上之構造。 上述平均值係在5處以上測定每10μm的細孔數之算術平均值。 本發明中，所謂「細孔」係意指孔徑5μm以下的開氣孔(與外氣連接的細孔)。細孔的孔徑係在細孔入口所測定的值。 The term “porous structure” in the present invention refers to a structure in which pores exist when a cross-section of the electroplated layer is cut along the thickness direction, and the average number of pores observed per 10 μm of the cross-section is 5 or more. The above average value is the arithmetic average of the number of pores per 10 μm measured at 5 or more places. In the present invention, "pores" mean open pores (pores connected to outside air) with a pore diameter of 5 μm or less. The pore diameter is a value measured at the pore entrance.
電鍍層可由1層電鍍層構成，亦可含有2層以上的電鍍層。 含有2層以上電鍍層的電鍍層可舉例如含有：1層以上的基底電鍍層、以及配置於基底電鍍層上且表面具有多孔質構造的電鍍層；如此之電鍍層。 The electroplating layer may consist of one electroplating layer, or may contain two or more electroplating layers. Examples of a plating layer including two or more plating layers include: one or more base plating layers, and a plating layer disposed on the base plating layer and having a porous structure on the surface; such a plating layer.
電鍍層的材質並無特別的限制，可考量構造體的用途、基材的材質等而選擇。電鍍層的材質具體而言可舉例如：鎳、銅、錫、鋅、鉻等。 當電鍍層係由2層以上電鍍層構成的情形時，2層以上電鍍層的材質可為相同、亦可為不同。 The material of the plating layer is not particularly limited and can be selected taking into consideration the use of the structure, the material of the base material, etc. Specific examples of the material of the plating layer include nickel, copper, tin, zinc, chromium, and the like. When the electroplating layer is composed of two or more electroplating layers, the materials of the two or more electroplating layers may be the same or different.
電鍍層具有的多孔質構造，較佳係具有：第1細孔、與在第1細孔表面所形成的第2細孔。The plating layer preferably has a porous structure having first pores and second pores formed on the surface of the first pores.
第1細孔的孔徑並無特別的限制。例如，第1細孔的平均孔徑亦可在0.1μm~5μm的範圍。 第1細孔的深度並無特別的限制。例如，第1細孔的平均深度亦可在0.1μm~5μm的範圍。 The pore diameter of the first pores is not particularly limited. For example, the average pore diameter of the first pores may be in the range of 0.1 μm to 5 μm. The depth of the first pore is not particularly limited. For example, the average depth of the first pores may be in the range of 0.1 μm to 5 μm.
第2細孔的孔徑並無特別的限制。例如，第2細孔的平均孔徑亦可在5nm~500nm的範圍。 第2細孔的深度並無特別的限制。例如，第2細孔的平均深度亦可在5nm~300nm的範圍。 The pore diameter of the second pores is not particularly limited. For example, the average pore diameter of the second pores may be in the range of 5 nm to 500 nm. The depth of the second pores is not particularly limited. For example, the average depth of the second pores may be in the range of 5 nm to 300 nm.
本發明中，細孔的孔徑及深度係利用影像解析法所測定。例如，將電鍍層沿厚度方向切斷，利用電子顯微鏡等觀察所獲得截面並測定。 本發明中，細孔的平均孔徑與平均深度係針對80個細孔所測得值的算術平均值。 In the present invention, the pore diameter and depth of the pores are measured using an image analysis method. For example, the electroplated layer is cut in the thickness direction, and the obtained cross section is observed and measured using an electron microscope or the like. In the present invention, the average pore diameter and average depth of pores are the arithmetic mean of values measured for 80 pores.
設有具第1細孔、與在第1細孔表面所形成的第2細孔的多孔質構造之電鍍層，例如可藉由形成具有第1細孔的電鍍層，接著在第1細孔的表面形成第2細孔而可獲得。An electroplating layer having a porous structure having first pores and second pores formed on the surface of the first pores can be formed, for example, by forming the electroplating layer having the first pores and then forming the first pores in the plating layer. It can be obtained by forming the second pores on the surface.
具有第1細孔的電鍍層係例如使用經添加妨礙電鍍層成長物質的電鍍液以形成電鍍層，接著除去妨礙電鍍層成長的物質，而可形成。此種方法可舉例如日本專利第5366076號所記載方法。The plating layer having the first pores can be formed, for example, by using a plating solution to which a substance that inhibits the growth of the plating layer is added to form the plating layer, and then removing the substance that inhibits the growth of the plating layer. An example of such a method is the method described in Japanese Patent No. 5366076.
妨礙電鍍層成長的物質可舉例如：溶解於電鍍液中呈陽離子性，且利用還原分解生成非水溶性分解物的物質。溶解於電鍍液中呈陽離子性，且利用還原分解生成非水溶性分解物的物質，若施行電鍍，則會被吸附於成為陰極的被鍍物，並在被鍍物表面被還原分解而生成非水溶性分解物。該非水溶性分解物會殘留於被鍍物中，而妨礙電鍍層的成長。Examples of substances that hinder the growth of the plating layer include substances that are cationic when dissolved in the plating solution and decompose by reduction to produce water-insoluble decomposition products. Substances that are cationic when dissolved in the plating solution and decompose by reduction to form non-water-soluble decomposition products will be adsorbed to the plated object that becomes the cathode when electroplating is performed, and will be reduced and decomposed on the surface of the plated object to form non-water-soluble decomposition products. Water-soluble decomposition products. This water-insoluble decomposition product will remain in the object to be plated and hinder the growth of the plating layer.
在電鍍液中呈陽離子性、且利用還原分解生成非水溶性分解物的物質，可舉例如：具有如烷基、芳基、芳烷基般之疏水性基的水溶性四級銨化合物。Substances that are cationic in the plating solution and decompose by reduction to produce water-insoluble decomposition products include, for example, water-soluble quaternary ammonium compounds having a hydrophobic group such as an alkyl group, an aryl group, or an aralkyl group.
具有疏水性基的水溶性四級銨化合物，具體而言可舉例如：十二烷基三甲銨、十四烷基三甲銨、十六烷基三甲銨、十八烷基三甲銨、苯基三甲銨、苄基三甲銨、苄基三乙銨、苄基三丁銨、二癸基二甲銨、十二烷基二甲基苄銨、十四烷基二甲基苄銨、十八烷基二甲基苄銨、三辛基甲銨、十二烷基吡啶鎓或苄基吡啶鎓的氯化物、溴化物、氫氧化物、硫酸鹽及硝酸鹽。 電鍍液中所含具有疏水性基的水溶性四級銨化合物可僅為1種、亦可為2種以上。 Water-soluble quaternary ammonium compounds having a hydrophobic group include, specifically, dodecyltrimethylammonium, tetradecyltrimethylammonium, cetyltrimethylammonium, octadecyltrimethylammonium, and phenyltrimethylammonium. Ammonium, benzyltrimethylammonium, benzyltriethylammonium, benzyltributylammonium, didecyldimethylammonium, dodecyldimethylbenzylammonium, tetradecyldimethylbenzylammonium, octadecyl Chlorides, bromides, hydroxides, sulfates and nitrates of dimethylbenzylammonium, trioctylmethane, dodecylpyridinium or benzylpyridinium. The plating solution may contain only one type of water-soluble quaternary ammonium compound having a hydrophobic group, or two or more types.
從充分獲得妨礙電鍍層成長之效果的觀點而言，電鍍液中所含具有疏水性基的水溶性四級銨化合物之含量較佳係0.001mol/L以上。從形成均勻之電鍍層的觀點，電鍍液中所含具有疏水性基的水溶性四級銨化合物之含量較佳係0.1mol/L以下。From the viewpoint of fully obtaining the effect of inhibiting the growth of the plating layer, the content of the water-soluble quaternary ammonium compound having a hydrophobic group contained in the plating solution is preferably 0.001 mol/L or more. From the viewpoint of forming a uniform electroplating layer, the content of the water-soluble quaternary ammonium compound having a hydrophobic group contained in the electroplating solution is preferably 0.1 mol/L or less.
電鍍層形成時所使用的電鍍液之種類並無特別的限制，可從公知電鍍液中選擇。電鍍液具體而言可舉例如：瓦特浴(Watts bath)、伍茨浴(Wood bath)、磺胺酸鎳浴、有機酸鎳浴等電鍍鎳浴；硫酸銅浴、焦磷酸銅浴、硫酸錫浴、甲磺酸錫浴、氯化鋅浴、硫酸鋅浴、各種合金鍍浴等。The type of plating solution used when forming the plating layer is not particularly limited, and it can be selected from known plating solutions. Specific examples of the electroplating solution include electroplating nickel baths such as Watts bath, Wood bath, sulfamate nickel bath, and organic acid nickel bath; copper sulfate bath, copper pyrophosphate bath, and tin sulfate bath , tin methanesulfonate bath, zinc chloride bath, zinc sulfate bath, various alloy plating baths, etc.
在第1細孔表面的第2細孔之形成，係例如使具有第1細孔的電鍍層表面與蝕刻液接觸而可實施。蝕刻液的種類並無特別的限制。例如，亦可含有氧化劑與無機酸。蝕刻液亦可為氧化劑與無機酸的水溶液。The second pores on the surface of the first pores can be formed, for example, by bringing the surface of the plating layer having the first pores into contact with an etching liquid. The type of etching liquid is not particularly limited. For example, an oxidizing agent and an inorganic acid may be included. The etching solution may also be an aqueous solution of an oxidizing agent and an inorganic acid.
氧化劑可舉例如：硝酸、過錳酸、過氧化氫等。蝕刻液中的氧化劑之濃度並無特別的限制。例如，蝕刻液中的氧化劑之濃度可從0.1質量%~20質量%中選擇，較佳係0.5質量%~5質量%。 無機酸可舉例如：磷酸、硫酸、鹽酸等。蝕刻液中的無機酸之濃度並無特別的限制。例如，蝕刻液中的無機酸之濃度可從0.1質量%~20質量%中選擇，較佳係5質量%~10質量%。 Examples of the oxidizing agent include nitric acid, permanganic acid, hydrogen peroxide, and the like. The concentration of the oxidizing agent in the etching solution is not particularly limited. For example, the concentration of the oxidant in the etching solution can be selected from 0.1 mass% to 20 mass%, and preferably 0.5 mass% to 5 mass%. Examples of inorganic acids include phosphoric acid, sulfuric acid, and hydrochloric acid. The concentration of the inorganic acid in the etching solution is not particularly limited. For example, the concentration of the inorganic acid in the etching solution can be selected from 0.1 mass% to 20 mass%, and preferably 5 mass% to 10 mass%.
與電鍍層表面接觸時的蝕刻液之溫度並無特別的限制。例如，蝕刻液之溫度可從20℃~60℃的範圍選擇，較佳係30℃~50℃。The temperature of the etching solution when in contact with the surface of the plating layer is not particularly limited. For example, the temperature of the etching liquid can be selected from the range of 20°C to 60°C, preferably 30°C to 50°C.
使電鍍層表面與蝕刻液接觸的時間並無特別的限制。例如，可從30秒鐘~10分鐘的範圍選擇，較佳係1分鐘~5分鐘。There is no particular limit on the time for which the electroplated layer surface is brought into contact with the etching liquid. For example, it can be selected from the range of 30 seconds to 10 minutes, preferably 1 minute to 5 minutes.
電鍍層設有多孔質構造的表面之突出谷部深度(Rvk)，較佳係0.3μm以上、更佳係0.4μm以上、又更佳係0.5μm以上。 從使電鍍層設有多孔質構造的表面與樹脂構件接合時樹脂進入細孔之容易度的觀點而言，電鍍層設有多孔質構造的表面之突出谷部深度(Rvk)較佳係1.5μm以下。 The protruding valley depth (Rvk) of the surface of the electroplated layer having a porous structure is preferably 0.3 μm or more, more preferably 0.4 μm or more, and still more preferably 0.5 μm or more. From the viewpoint of the ease with which resin can enter the pores when the surface of the plating layer has a porous structure is joined to a resin member, the protruding valley depth (Rvk) of the surface of the plating layer having a porous structure is preferably 1.5 μm. the following.
在本發明中，電鍍層具有多孔質構造之面的突出谷部深度(Rvk)係根據JIS B 0671-2：2002(ISO 13565-2：1996)所測定的值。In the present invention, the protruding valley depth (Rvk) of the surface of the plating layer having a porous structure is a value measured in accordance with JIS B 0671-2:2002 (ISO 13565-2:1996).
電鍍層設有多孔質構造的表面之最大高度(Rz)，較佳係1.5μm以上、更佳係2μm以上。 從使電鍍層設有多孔質構造的表面與樹脂構件接合時樹脂進入細孔之容易度的觀點而言，電鍍層設有多孔質構造的表面之最大高度(Rz)較佳係在電鍍層的厚度以下，更佳係例如10μm以下、或5μm以下。 The maximum height (Rz) of the surface of the plating layer having a porous structure is preferably 1.5 μm or more, more preferably 2 μm or more. From the viewpoint of the ease with which resin can enter the pores when the surface of the plating layer has the porous structure is joined to the resin member, the maximum height (Rz) of the surface of the plating layer having the porous structure is preferably set to The thickness is less than or equal to 10 μm or less, more preferably 10 μm or less, or 5 μm or less.
電鍍層設有多孔質構造的表面之算術平均粗糙度(Ra)，較佳係0.2μm以上、更佳係0.3μm以上。 從使電鍍層設有多孔質構造的表面與樹脂構件接合時樹脂進入細孔之容易度的觀點而言，電鍍層設有多孔質構造的表面之算術平均粗糙度(Ra)較佳係5μm以下，更佳係3μm以下、1μm以下、或0.7μm以下。 The arithmetic mean roughness (Ra) of the surface of the electroplated layer having a porous structure is preferably 0.2 μm or more, more preferably 0.3 μm or more. From the viewpoint of the ease with which resin can enter pores when the surface of the plating layer has a porous structure is joined to a resin member, the arithmetic mean roughness (Ra) of the surface of the plating layer having a porous structure is preferably 5 μm or less. , more preferably 3 μm or less, 1 μm or less, or 0.7 μm or less.
電鍍層設有多孔質構造的表面，利用氪吸附法所測得實際表面積(m 2)除以幾何表面積(m 2)獲得的粗糙度指數，較佳係12以上、更佳係13以上、又更佳係14以上。 The surface of the electroplated layer has a porous structure. The roughness index obtained by dividing the actual surface area (m 2 ) measured by the krypton adsorption method by the geometric surface area (m 2 ) is preferably 12 or more, more preferably 13 or more, and further Preferably 14 or above.
在本發明中，電鍍層設有多孔質構造的表面之實際表面積，係以氪氣為吸附質，並利用BET法求取。亦即，測定對象的BET比表面積(m 2/g)乘上測定對象的質量(g)的值，即為測定對象的實際表面積(m 2)。電鍍層設有多孔質構造的表面之實際表面積係例如依照實施例所記載方法來求取。 In the present invention, the actual surface area of the surface of the electroplated layer provided with a porous structure is determined using the BET method using krypton gas as the adsorbent. That is, the actual surface area (m 2 ) of the measurement object is the value obtained by multiplying the BET specific surface area (m 2 /g) of the measurement object by the mass ( g ) of the measurement object. The actual surface area of the surface of the electroplated layer provided with the porous structure is determined, for example, according to the method described in the Examples.
在本發明中，電鍍層設有多孔質構造的表面之幾何表面積，係由測定對象的尺寸所求得的值。例如，由具有多孔質構造之電鍍層全面覆蓋的測定對象係長度X、寬度Y、高度Z的立方體時，幾何表面積S便以S=2XY+2YZ+2ZX之形式求得。In the present invention, the geometric surface area of the surface of the plating layer provided with the porous structure is a value obtained from the dimensions of the measurement object. For example, when the measurement object is a cube with length
本發明之構造體的用途並無特別的限制。例如，除了後述接合體之外，尚可舉例如抗菌構件、匯流排等。亦即，本發明之實施形態係包括有含有本發明之構造體的接合體、抗菌構件、匯流排等物品。 本發明中所謂「抗菌構件」係意指呈抗菌性能的構件。本發明的「抗菌性能」係包括有：使細菌滅亡或抑制增殖的性能(抗細菌性能)、以及使病毒去活化的性能(抗病毒性能)。亦即，抗菌性能的對象係包括有細菌與病毒。 The use of the structure of the present invention is not particularly limited. For example, in addition to the joint body described later, antibacterial members, busbars, etc. may be mentioned. That is, embodiments of the present invention include articles such as joints, antibacterial members, and busbars containing the structure of the present invention. The so-called "antibacterial member" in the present invention means a member with antibacterial properties. The "antibacterial performance" of the present invention includes the performance of killing bacteria or inhibiting their proliferation (antibacterial performance), and the performance of deactivating viruses (antiviral performance). That is, the target systems of antibacterial properties include bacteria and viruses.
本發明的構造體呈抗菌性能的機制係例如可被推測為如下。惟，本發明之範圍並不因該推測而受任何限定。 本發明的構造體係被配置於基材上的電鍍層具有多孔質構造。所以，當細菌附著於電鍍層時，會利用電鍍層的多孔質構造損傷細菌的細胞壁，較佳態樣認為係細菌滅亡。 病毒附著於電鍍層時，電鍍層的多孔質構造所捕捉到的病毒之活性減弱，較佳態樣認為係病毒去活化。 再者，本發明的構造體由於電鍍層具有多孔質構造，因而電鍍層的微觀表面積較大。所以，可於有限面積附著大量的細菌或病毒，而有效地發揮抗菌作用。 The mechanism by which the structure of the present invention exhibits antibacterial properties can be presumed as follows, for example. However, the scope of the present invention is not limited in any way by this speculation. In the structural system of the present invention, the plating layer arranged on the base material has a porous structure. Therefore, when bacteria adhere to the electroplating layer, they will use the porous structure of the electroplating layer to damage the cell wall of the bacteria, and it is better to think that the bacteria will die. When the virus adheres to the electroplating layer, the activity of the virus captured by the porous structure of the electroplating layer is weakened. It is better to think that the virus is deactivated. Furthermore, since the electroplated layer of the structure of the present invention has a porous structure, the microscopic surface area of the electroplated layer is large. Therefore, a large number of bacteria or viruses can be attached to a limited area and effectively exert an antibacterial effect.
抗菌構件可使用作為例如：醫療・醫藥用品(醫療用墊、手術器具、藥品用瓶的蓋、牙科材料等)；住宅關聯用品(門把、扶手等)；食品・調理關聯用品(餐具、調理器具、水槽、水龍頭、配膳用托盤等)；基礎設施關聯用品(水處理或工廠設施所使用的配管等)；汽車關聯用品(門把等)；雜貨類(筆袋、尺規、自動鉛筆、計算機等)；電子機器類(個人電腦、智慧手機等)；及娛樂關聯用品(遊戲機所使用的代幣等)等各種物品。Antibacterial members can be used as, for example: medical and pharmaceutical products (medical pads, surgical instruments, pharmaceutical bottle caps, dental materials, etc.); housing-related products (doorknobs, handrails, etc.); food and cooking-related products (tableware, cooking utensils, etc.) utensils, sinks, faucets, meal trays, etc.); infrastructure-related supplies (water treatment or piping used in factory facilities, etc.); automobile-related supplies (door handles, etc.); groceries (pen bags, rulers, mechanical pencils, etc.) computers, etc.); electronic equipment (personal computers, smartphones, etc.); and entertainment-related supplies (tokens used in game consoles, etc.) and other various items.
＜構造體之製造方法＞ 本發明的構造體之製造方法，係包括有： 在基材上形成具有多孔質構造之電鍍層的步驟；以及 使上述電鍍層的表面與蝕刻液接觸的步驟。 ＜How to make a structure＞ The manufacturing method of the structure of the present invention includes: The step of forming an electroplating layer with a porous structure on a substrate; and The step of bringing the surface of the electroplated layer into contact with the etching liquid.
根據上述方法，可製造無論基材的材質如何均於表面具有微細凹凸構造的構造體。 上述方法中，在基材上形成具有多孔質構造之電鍍層的步驟，例如可使用如上述般添加妨礙電鍍層成長之物質的電鍍液實施。使具有多孔質構造的電鍍層表面與蝕刻液相接觸的步驟，例如可使用含有氧化劑與無機酸的蝕刻液來實施。 According to the above method, a structure having a fine uneven structure on the surface can be produced regardless of the material of the base material. In the above method, the step of forming a plating layer having a porous structure on the base material can be performed, for example, using a plating solution containing a substance that inhibits the growth of the plating layer as described above. The step of bringing the surface of the electroplated layer having a porous structure into contact with the etching liquid can be carried out using, for example, an etching liquid containing an oxidizing agent and an inorganic acid.
上述方法的基材、電鍍層及蝕刻液之詳細內容及較佳態樣，係與有關本發明之構造體所記載的電鍍層與蝕刻液之詳細內容及較佳態樣相同。 亦即，本發明之方法亦可為上述本發明的構造體之製造方法。 The details and preferred aspects of the base material, plating layer, and etching solution in the above method are the same as the details and preferred aspects of the plating layer and etching solution described in relation to the structure of the present invention. That is, the method of this invention may also be the manufacturing method of the structure of this invention mentioned above.
＜接合體＞ 本發明的接合體係具有：上述本發明的構造體、以及接合於上述構造體形成有上述電鍍層之面的樹脂構件；如此所成之接合體。 ＜Joint＞ The bonding system of the present invention includes: the structure of the present invention; a resin member bonded to the surface of the structure on which the plating layer is formed; and the bonded body thus formed.
本發明中，所謂構造體與樹脂構件呈「接合」的狀態，係指構造體未使用接著劑、螺絲等而與樹脂構件呈固著的狀態。In the present invention, the state in which the structure and the resin member are "joined" means that the structure is fixed to the resin member without using adhesives, screws, or the like.
構造體與樹脂構件呈接合的狀態，係例如將利用熔融或軟化而具有流動性之狀態的樹脂構件材料，賦予至構造體經粗化處理的表面而可形成。若樹脂構件材料具有流動性之狀態，則樹脂構件材料滲入構造體表面的多孔質構造而顯現出錨定效應，樹脂構件則牢固地接合於構造體表面。The structure and the resin member are in a joined state, for example, by applying a resin member material in a fluid state due to melting or softening to the roughened surface of the structure. If the resin member material is in a fluid state, the resin member material penetrates into the porous structure on the surface of the structure and exhibits an anchoring effect, and the resin member is firmly bonded to the surface of the structure.
樹脂構件所含樹脂的種類並無特別的限制，可為熱可塑性樹脂、熱硬化性樹脂、熱可塑性彈性體、熱硬化性彈性體等。 熱可塑性樹脂可舉例如：聚乙烯(PE)、聚丙烯(PP)、聚苯乙烯(PS)、丙烯腈/苯乙烯樹脂(AS)、丙烯腈/丁二烯/苯乙烯樹脂(ABS)、甲基丙烯酸樹脂(PMMA)、聚氯乙烯(PVC)、聚醯胺(PA)、聚縮醛(POM)、超高分子量聚乙烯(UHPE)、聚對苯二甲酸丁二酯(PBT)、聚對苯二甲酸乙二酯(PET)、聚甲基戊烯(TPX)、聚碳酸酯(PC)、改質聚苯醚(PPE)、聚苯硫醚(PPS)、聚醚醚酮(PEEK)、液晶性樹脂(LCP)、聚四氟乙烯(PTFE)、聚醚醯亞胺(PEI)、聚芳酯(PAR)、聚碸(PSF)、聚醚碸(PES)、聚醯胺醯亞胺(PAI)等。 熱硬化性樹脂可舉例如：酚樹脂、脲樹脂、三聚氰胺樹脂、不飽和聚酯、醇酸樹脂、環氧樹脂、鄰苯二甲酸二烯丙酯等。 熱可塑性彈性體可舉例如：苯乙烯系熱可塑性彈性體、聚酯系熱可塑性彈性體、胺甲酸乙酯系熱可塑性彈性體、醯胺系熱可塑性彈性體等。 熱硬化性彈性體可舉例如：天然橡膠(NR)、異戊二烯橡膠(IR)、丁二烯橡膠(BR)、苯乙烯-丁二烯共聚合體橡膠(SBR)、氯丁二烯橡膠(CR)、丙烯腈-丁二烯共聚合體橡膠(NBR)等二烯系橡膠；丁基橡膠(IIR)、乙烯・丙烯橡膠(EPM)、胺甲酸乙酯橡膠、聚矽氧橡膠、丙烯酸橡膠等非二烯系橡膠等等。 樹脂構件所含的樹脂亦可呈離子聚合物或高分子合金的狀態。 樹脂構件所含樹脂可僅為1種、亦可為2種以上。 The type of resin contained in the resin member is not particularly limited, and may be thermoplastic resin, thermosetting resin, thermoplastic elastomer, thermosetting elastomer, or the like. Examples of thermoplastic resins include polyethylene (PE), polypropylene (PP), polystyrene (PS), acrylonitrile/styrene resin (AS), acrylonitrile/butadiene/styrene resin (ABS), Methacrylic resin (PMMA), polyvinyl chloride (PVC), polyamide (PA), polyacetal (POM), ultra-high molecular weight polyethylene (UHPE), polybutylene terephthalate (PBT), Polyethylene terephthalate (PET), polymethylpentene (TPX), polycarbonate (PC), modified polyphenylene ether (PPE), polyphenylene sulfide (PPS), polyether ether ketone ( PEEK), liquid crystal resin (LCP), polytetrafluoroethylene (PTFE), polyetherimide (PEI), polyarylate (PAR), polystyrene (PSF), polyetherstyrene (PES), polyamide acyl imine (PAI), etc. Examples of the thermosetting resin include phenol resin, urea resin, melamine resin, unsaturated polyester, alkyd resin, epoxy resin, diallyl phthalate, and the like. Examples of the thermoplastic elastomer include styrene-based thermoplastic elastomers, polyester-based thermoplastic elastomers, urethane-based thermoplastic elastomers, and amide-based thermoplastic elastomers. Examples of the thermosetting elastomer include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene copolymer rubber (SBR), and chloroprene rubber. (CR), acrylonitrile-butadiene copolymer rubber (NBR) and other diene rubbers; butyl rubber (IIR), ethylene propylene rubber (EPM), urethane rubber, silicone rubber, acrylic rubber and other non-diene rubbers, etc. The resin contained in the resin member may also be in the state of an ion polymer or a polymer alloy. The resin member may contain only one type of resin or two or more types of resin.
樹脂構件除了樹脂之外，亦可含有各種摻合劑。摻合劑可舉例如：玻璃纖維、碳纖維、無機粉末等填充材；熱安定劑、抗氧化劑、顏料、耐候劑、難燃劑、可塑劑、分散劑、滑劑、離型劑、抗靜電劑等。The resin member may contain various admixtures in addition to resin. Examples of admixtures include: fillers such as glass fiber, carbon fiber, and inorganic powder; thermal stabilizers, antioxidants, pigments, weathering agents, flame retardants, plasticizers, dispersants, lubricants, release agents, antistatic agents, etc. .
當樹脂構件含有樹脂以外的成分時，樹脂佔樹脂構件全體的比例較佳係10質量%以上、更佳係20質量%以上、又更佳係30質量%以上。When the resin member contains components other than resin, the proportion of resin in the entire resin member is preferably 10 mass% or more, more preferably 20 mass% or more, and still more preferably 30 mass% or more.
在構造體具有多孔質構造之面接合樹脂構件的步驟，例如可利用射出成形等公知方法來實施。 [實施例] The step of joining the resin member to the surface of the structure having a porous structure can be carried out by a known method such as injection molding. [Example]
以下，針對本發明的實施形態參照實施例進行說明。另外，本發明並不被侷限於該等實施例的記載。Hereinafter, embodiments of the present invention will be described with reference to Examples. In addition, the present invention is not limited to the description of these examples.
＜實施例1＞ (1)接合體之製作 在基材之鋁板表面形成厚度約3~4μm的基底鍍鎳層。 基底鍍鎳層係將含有硫酸鎳(280g/L)、氯化鎳(45g/L)、及硼酸(40g/L)的水溶液使用作為電鍍液，以液溫50℃、pH4.3、陰極電流密度3A/dm 2的條件實施。 <Example 1> (1) Preparation of joint body A base nickel plating layer with a thickness of about 3 to 4 μm was formed on the surface of the aluminum plate as the base material. The base nickel plating layer uses an aqueous solution containing nickel sulfate (280g/L), nickel chloride (45g/L), and boric acid (40g/L) as the plating solution, with a liquid temperature of 50°C, a pH of 4.3, and a cathode current of The conditions of density 3A/dm 2 are implemented.
其次，在基底鍍鎳層上形成厚度約1~5μm之具有多孔質構造的鍍鎳層。Secondly, a nickel plating layer with a thickness of about 1 to 5 μm and a porous structure is formed on the base nickel plating layer.
具有多孔質構造的鍍鎳層係使用：在含有硫酸鎳(280g/L)、氯化鎳(45g/L)、及硼酸(40g/L)的水溶液中添加作為妨礙電鍍層成長之物質的十二烷基三甲氯化銨(10ml/L)所成的電鍍液，以液溫50℃、pH4.3、陰極電流密度3A/dm 2的條件實施。 The nickel plating layer with a porous structure is made by adding a substance that hinders the growth of the plating layer to an aqueous solution containing nickel sulfate (280g/L), nickel chloride (45g/L), and boric acid (40g/L). The electroplating solution made of dialkyltrimethylammonium chloride (10 ml/L) was implemented under the conditions of liquid temperature 50°C, pH 4.3, and cathode current density 3A/dm 2 .
對已形成具有多孔質構造之鍍鎳層的鋁板，在含硝酸0.6質量%與磷酸7.5質量%的水溶液(40℃)中浸漬3分鐘，而施行蝕刻處理。The aluminum plate on which the nickel plating layer having a porous structure was formed was immersed in an aqueous solution (40° C.) containing 0.6 mass% nitric acid and 7.5 mass% phosphoric acid for 3 minutes to perform an etching process.
將施行鍍鎳層之蝕刻處理後的鋁板，設置於日本製鋼所製之射出成形機(J55-AD)所裝設的小型啞鈴金屬嵌入模具內。接著，於模具內將聚苯硫醚(PPS、東曹股份有限公司、SUSTEEL SGX120)射出成形，而製作在鍍鎳層上形成PPS層的接合體A。The etched aluminum plate with nickel plating is placed in a small dumbbell metal insert mold installed in an injection molding machine (J55-AD) manufactured by Nippon Steel. Next, polyphenylene sulfide (PPS, Tosoh Co., Ltd., SUSTEEL SGX120) was injection molded in a mold to produce a joint body A in which a PPS layer was formed on the nickel plating layer.
(2)鍍鎳層觀察 接合體A於厚度方向被切斷所得的截面，其電子顯微鏡影像被示於圖1，且圖1的部分放大影像被示於圖2。 圖中亮度相對較高的部分係相當於鍍鎳層。 如圖1與圖2所示，可觀察到鍍鎳層係在與鋁板的相反側表面設有多孔質構造，且多孔質構造係呈具有第1細孔、與在第1細孔表面所形成的第2細孔之模樣。 (2) Observation of nickel plating layer The electron microscope image of the cross section of the joint body A cut in the thickness direction is shown in FIG. 1 , and the partially enlarged image of FIG. 1 is shown in FIG. 2 . The relatively bright part in the picture corresponds to the nickel plating layer. As shown in Figures 1 and 2, it can be observed that the nickel plating layer has a porous structure on the surface opposite to the aluminum plate, and the porous structure has first pores and is formed on the surface of the first pores. The appearance of the second pore.
從圖1與圖2所示影像可測定到第1細孔每10μm的平均個數係6個，第1細孔的平均孔徑係0.97μm，第1細孔的平均深度係1.5μm。From the images shown in Figures 1 and 2, it can be determined that the average number of first pores per 10 μm is 6, the average pore diameter of the first pores is 0.97 μm, and the average depth of the first pores is 1.5 μm.
(3)表面粗糙度 在接合體A之製作時，於形成PPS層之前，使用數位式顯微鏡(DSX510、Olympus股份有限公司製)，根據JIS B 0671-2：2002(ISO 13565-2：1996)測定具有多孔質構造之鍍鎳層的突出谷部深度(Rvk)。其結果被示於表1。 在接合體A之製作時，於形成PPS層之前，使用測定裝置數位式顯微鏡(DSX510、Olympus股份有限公司製)，根據JIS B 0601-2001(ISO 4287-1997)測定具有多孔質構造之鍍鎳層的最大高度(Rz)與算術平均粗糙度(Ra)。其結果被示於表1。 (3)Surface roughness When producing the joint body A, before forming the PPS layer, a digital microscope (DSX510, manufactured by Olympus Co., Ltd.) was used to measure the porous structure according to JIS B 0671-2:2002 (ISO 13565-2:1996). Protruding valley depth (Rvk) of the nickel plating layer. The results are shown in Table 1. When producing the joint body A, before forming the PPS layer, a measuring device digital microscope (DSX510, manufactured by Olympus Co., Ltd.) was used to measure the nickel plating with a porous structure in accordance with JIS B 0601-2001 (ISO 4287-1997). The maximum height of the layer (Rz) and the arithmetic mean roughness (Ra). The results are shown in Table 1.
(4)粗糙度指數 對已形成具有多孔質構造鍍鎳層後的鋁板(形成PPS層前)，利用真空加熱脫氣(100℃)實施前處理，使用比表面積測定裝置(BELSORP-max、MicrotracBEL股份有限公司製)，利用液態氮溫度下(77K)的氪氣吸附法，測定吸脫附等溫線。從所獲得結果求取試驗片的BET比表面積。將所獲得BET比表面積(m 2/g)乘上質量(g)的值設為實際表面積(m 2)，再將實際表面積除以鋁板的幾何表面積(m 2)而求取粗糙度指數。其結果被示於表1。 (4) Roughness index The aluminum plate after the nickel plating layer with a porous structure has been formed (before the PPS layer is formed) is pre-processed by vacuum heating and degassing (100°C), and a specific surface area measuring device (BELSORP-max, MicrotracBEL Co., Ltd.), uses the krypton gas adsorption method at liquid nitrogen temperature (77K) to measure the adsorption-desorption isotherm. The BET specific surface area of the test piece was calculated from the obtained results. The value obtained by multiplying the obtained BET specific surface area (m 2 /g) by the mass (g) is set as the actual surface area (m 2 ), and then the actual surface area is divided by the geometric surface area (m 2 ) of the aluminum plate to obtain the roughness index. The results are shown in Table 1.
(5)接合強度 接合體A的鍍鎳層與PPS層之剪切接合強度，係依照根據ISO19095的方法所測定。 具體而言，在拉伸試驗機(型號1323、AIKOH ENGINEERING公司製)上安裝專用夾具，於室溫(23℃)下，以夾具間距離60mm、拉伸速度10mm/min的條件施行斷裂荷重(N)之測定。 藉由將所測得斷裂荷重(N)除以鍍鎳層與PPS層間之接合部分的面積(50mm 2)，而獲得剪切接合強度(MPa)。其結果被示於表1。 (5) Joint strength The shear joint strength of the nickel plating layer and the PPS layer of the joint body A was measured according to the method in accordance with ISO19095. Specifically, a special clamp was installed on a tensile testing machine (model 1323, manufactured by AIKOH ENGINEERING Co., Ltd.), and the breaking load ( Determination of N). The shear bonding strength (MPa) was obtained by dividing the measured breaking load (N) by the area of the bonding portion between the nickel plating layer and the PPS layer (50 mm 2 ). The results are shown in Table 1.
(6)氣密性 將鍍鎳層施行蝕刻處理後的鋁板，設置於在日本製鋼所製之射出成形機(J55-AD)所裝設的He洩漏金屬嵌入模具內。接著，於模具內將聚苯硫醚(PPS、東曹股份有限公司、SUSTEEL SGX120)射出成形，而製作在鍍鎳層上形成PPS層的接合體B。 接著，針對試驗片B的He洩漏性依照根據ISO19095的方法施行評價。具體而言，將依上述所獲得試驗片安裝於可密閉的專用夾具上，在密閉的空間中對He氣體施加0.1MPa壓力，利用He氣體檢測器(CANON ANELVA製、HELEN M-222LD)，依正壓吸附法測定通過試驗片的He氣體流量。 從開始施加壓力5分鐘後所檢測到的He氣體流量，若為10 -6[Pa・m 3/s]以下則評為「〇」、若為10 -5[Pa・m 3/s]以上則評為「×」，依此評價氣密性。其結果被示於表1。 (6) Airtightness An aluminum plate after etching the nickel plating layer was placed in a He leakage metal insert mold installed in an injection molding machine (J55-AD) manufactured by Nippon Steel. Next, polyphenylene sulfide (PPS, Tosoh Co., Ltd., SUSTEEL SGX120) was injection molded in a mold to produce a joint B in which a PPS layer was formed on the nickel plating layer. Next, the He leakage property of the test piece B was evaluated according to the method in accordance with ISO19095. Specifically, the test piece obtained as described above was mounted on a sealable special jig, a pressure of 0.1 MPa was applied to the He gas in a sealed space, and a He gas detector (HELEN M-222LD manufactured by CANON ANELVA) was used. The He gas flow rate passing through the test piece was measured by the positive pressure adsorption method. The He gas flow rate detected 5 minutes after the start of pressure application is rated as "0" if it is 10 -6 [Pa・m 3 /s] or less, and if it is 10 -5 [Pa・m 3 /s] or more Then it will be rated as "×", and the air tightness will be evaluated accordingly. The results are shown in Table 1.
＜實施例2＞ 除了將鍍鎳層之蝕刻處理時所使用的水溶液，變更為含有硝酸0.1質量%與磷酸0.1質量%的水溶液之外，與實施例1同樣地實施評價。其結果被示於表1。 觀察實施例2所獲得接合體A的截面，結果鍍鎳層係在與鋁板的相反側表面具有多孔質構造，且多孔質構造係具有第1細孔、與在第1細孔表面所形成的第2細孔。 <Example 2> Evaluation was performed in the same manner as in Example 1, except that the aqueous solution used for etching the nickel plating layer was changed to an aqueous solution containing 0.1 mass % nitric acid and 0.1 mass % phosphoric acid. The results are shown in Table 1. The cross-section of the joint A obtained in Example 2 was observed. It was found that the nickel plating layer had a porous structure on the surface opposite to the aluminum plate, and the porous structure had first pores and pores formed on the surface of the first pores. The 2nd pore.
＜實施例3＞ 除了將鍍鎳層之蝕刻處理時所使用的水溶液，變更為含有硝酸1質量%與磷酸20質量%的水溶液之外，與實施例1同樣地實施評價。其結果被示於表1。 觀察實施例3所獲得接合體A的截面，結果鍍鎳層係在與鋁板的相反側表面具有多孔質構造，且多孔質構造係具有第1細孔、與在第1細孔表面上所形成的第2細孔。 <Example 3> Evaluation was carried out in the same manner as in Example 1, except that the aqueous solution used for etching the nickel plating layer was changed to an aqueous solution containing 1 mass % of nitric acid and 20 mass % of phosphoric acid. The results are shown in Table 1. The cross-section of the joint A obtained in Example 3 was observed. It was found that the nickel plating layer had a porous structure on the surface opposite to the aluminum plate, and the porous structure had first pores and was formed on the surface of the first pores. The second pore.
＜實施例4＞ 除了將接合體之製作時所使用的樹脂，由PPS變更為聚丙烯(PP、Prime Polymer股份有限公司、Prime Polypro V7100)之外，與實施例1同樣地實施評價。其結果被示於表1。 觀察實施例4所獲得接合體A的截面，結果鍍鎳層係在與鋁板的相反側表面具有多孔質構造，且多孔質構造係具有第1細孔、與在第1細孔表面上所形成的第2細孔。 <Example 4> Evaluation was carried out in the same manner as in Example 1, except that the resin used in the preparation of the joined body was changed from PPS to polypropylene (PP, Prime Polymer Co., Ltd., Prime Polypro V7100). The results are shown in Table 1. The cross-section of the joint body A obtained in Example 4 was observed. It was found that the nickel plating layer had a porous structure on the surface opposite to the aluminum plate, and the porous structure had first pores and was formed on the surface of the first pores. The second pore.
＜實施例5＞ 除了將接合體之製作時所使用的樹脂，由PPS變更為聚鄰苯二甲醯胺(PPA、三井化學股份有限公司、ARLEN A350)之外，與實施例1同樣地實施評價。其結果被示於表1。 觀察實施例5所獲得接合體A的截面，結果鍍鎳層係在與鋁板的相反側表面具有多孔質構造，且多孔質構造係具有第1細孔、與在第1細孔表面上所形成的第2細孔。 <Example 5> Evaluation was performed in the same manner as in Example 1, except that the resin used in the preparation of the bonded body was changed from PPS to polyphthalamide (PPA, Mitsui Chemicals Co., Ltd., ARLEN A350). The results are shown in Table 1. The cross-section of the joint A obtained in Example 5 was observed. It was found that the nickel plating layer had a porous structure on the surface opposite to the aluminum plate, and the porous structure had first pores and was formed on the surface of the first pores. The second pore.
＜比較例1＞ 除了未施行鍍鎳層的蝕刻處理之外，與實施例1同樣地實施評價。其結果被示於表1。 將比較例1所製作的接合體A於厚度方向切斷所獲得的截面電子顯微鏡影像示於圖3，並將圖3的部分放大影像示於圖4。 圖中亮度相對較高的部分係相當於鍍鎳層。 如圖3與圖4所示，鍍鎳層雖在與鋁板的相反側表面具有多孔質構造，但在第1細孔的表面並沒有形成第2細孔。 ＜Comparative example 1＞ Evaluation was performed in the same manner as in Example 1 except that the nickel plating layer was not etched. The results are shown in Table 1. A cross-sectional electron microscope image obtained by cutting the joint body A produced in Comparative Example 1 in the thickness direction is shown in FIG. 3 , and a partially enlarged image of FIG. 3 is shown in FIG. 4 . The relatively bright part in the picture corresponds to the nickel plating layer. As shown in FIGS. 3 and 4 , the nickel plating layer has a porous structure on the surface opposite to the aluminum plate, but no second pores are formed on the surface of the first pores.
＜比較例2＞ 除了將接合體之製作時所使用的樹脂，由PPS變更為聚丙烯(PP、Prime Polymer股份有限公司、Prime Polypro V7100)之外，與比較例1同樣地實施評價。其結果被示於表1。 觀察比較例2所獲得接合體A的截面，結果鍍鎳層雖在與鋁板的相反側表面具有多孔質構造，但在第1細孔的表面並沒有形成第2細孔。 ＜Comparative example 2＞ Evaluation was carried out in the same manner as Comparative Example 1, except that the resin used in the preparation of the joined body was changed from PPS to polypropylene (PP, Prime Polymer Co., Ltd., Prime Polypro V7100). The results are shown in Table 1. The cross-section of the joint A obtained in Comparative Example 2 was observed. It was found that although the nickel plating layer had a porous structure on the surface opposite to the aluminum plate, no second pores were formed on the surface of the first pores.
＜比較例3＞ 除了將接合體之製作時所使用的樹脂，由PPS變更為聚鄰苯二甲醯胺(PPA、三井化學股份有限公司、ARLEN A350) 之外，與比較例1同樣地實施評價。其結果被示於表1。 觀察比較例3所獲得接合體A的截面，結果鍍鎳層雖在與鋁板的相反側表面具有多孔質構造，但在第1細孔的表面並沒有形成第2細孔。 ＜Comparative Example 3＞ Evaluation was carried out in the same manner as Comparative Example 1, except that the resin used in the preparation of the bonded body was changed from PPS to polyphthalamide (PPA, Mitsui Chemicals Co., Ltd., ARLEN A350). The results are shown in Table 1. Observation of the cross section of the joint A obtained in Comparative Example 3 revealed that although the nickel plating layer had a porous structure on the surface opposite to the aluminum plate, no second pores were formed on the surface of the first pores.
[表1]
(7)抗細菌性能 針對實施例1中形成具多孔質構造的鍍鎳層、且對鍍鎳層施行蝕刻處理的鋁板(試驗片A)，以及用於比較之未形成鍍鎳層的鋁板(試驗片B、表面粗糙度指數1.0)，實施乙醇滅菌。然後，根據ISO 21702：2019實施下述試驗。 具體而言，測定從在試驗片中接種細菌起30分鐘後與24小時後的生菌數比例。細菌係使用金黃色葡萄球菌，細菌濃度係設為2.5×10 5個/mL~10 6個/mL，培養液係設為1/25NB。其結果被示於表2。 (7) Antibacterial performance The aluminum plate (test piece A) on which a nickel-plated layer with a porous structure was formed and the nickel-plated layer was etched in Example 1, and the aluminum plate without a nickel-plated layer for comparison ( Test piece B, surface roughness index 1.0) was sterilized with ethanol. Then, perform the following tests according to ISO 21702:2019. Specifically, the ratio of the bacterial count 30 minutes and 24 hours after inoculation of bacteria in the test piece was measured. Staphylococcus aureus was used as the bacterial system, the bacterial concentration was set to 2.5×10 5 /mL to 10 6 /mL, and the culture medium was set to 1/25NB. The results are shown in Table 2.
30分鐘後的生菌數比例(%)，係表示從在試驗片中接種細菌時點經過30分鐘後的生菌數，相對於在試驗片中接種細菌時點的生菌數之比例。 24小時後的生菌數比例(%)，係表示從在試驗片中接種細菌時點經過24小時後的生菌數，相對於在試驗片中接種細菌時點的生菌數之比例。 The ratio of the number of bacteria after 30 minutes (%) represents the number of bacteria after 30 minutes from the time when bacteria are inoculated into the test piece, relative to the number of bacteria at the time when bacteria are inoculated into the test piece. The ratio of the number of bacteria after 24 hours (%) represents the number of bacteria after 24 hours from the time when bacteria are inoculated into the test piece, relative to the number of bacteria at the time when bacteria are inoculated into the test piece.
(8)抗病毒性能 使用抗細菌性能之試驗時所使用的試驗片A與試驗片B，根據ISO 21702：2019施行下述試驗。 具體而言，測定從在試驗片中接種病毒起30分鐘後與24小時後的病毒去活化率及感染力價。病毒係使用流感A H3N2(尺寸：80nm~120nm、具鞘膜)、及杯狀病毒(尺寸：27nm~32nm、無鞘膜)。 (8) Anti-virus performance Using the test piece A and test piece B used in the antibacterial performance test, the following test was performed in accordance with ISO 21702:2019. Specifically, the virus deactivation rate and infectivity value were measured 30 minutes and 24 hours after the virus was inoculated into the test piece. The viruses used were influenza A H3N2 (size: 80nm~120nm, with sheath membrane), and calicivirus (size: 27nm~32nm, without sheath membrane).
30分鐘後的病毒去活化率，係表示從在試驗片中接種病毒時點經過30分鐘後的感染力價，相對於在試驗片中接種病毒時點的感染力價之比例。 24小時後的病毒去活化率，係表示從在試驗片中接種病毒時點經過24小時後的感染力價，相對於在試驗片中接種病毒時點的感染力價之比例。 感染力價係表示病毒去活化程度的指標，利用TCID50(50% tissue culture infectious dose，半數組織細胞感染劑量)所測定的值。 The virus deactivation rate after 30 minutes represents the ratio of the infectivity value 30 minutes after the virus was inoculated into the test piece to the infectivity value at the time when the virus was inoculated into the test piece. The virus deactivation rate after 24 hours represents the ratio of the infectivity value 24 hours after the time when the virus is inoculated into the test piece to the infectivity value at the time when the virus is inoculated into the test piece. The infectivity value is an index indicating the degree of virus deactivation, and is a value measured using TCID50 (50% tissue culture infectious dose, half of the tissue culture infectious dose).
[表2]
如表2所示，在鋁板表面形成具有多孔質構造的鍍鎳層、且對鍍鎳層施行蝕刻處理所獲得的試驗片A，相較於未在鋁板表面形成具有多孔質構造的鍍鎳層的試驗片B之下，呈現較優異的抗細菌性能與抗病毒性能。As shown in Table 2, the test piece A obtained by forming a nickel plating layer with a porous structure on the surface of the aluminum plate and subjecting the nickel plating layer to an etching process was compared to a test piece A in which a nickel plating layer with a porous structure was not formed on the surface of the aluminum plate. Under the test piece B, it showed excellent antibacterial and antiviral properties.
日本專利申請第2022-045974號所揭示內容，藉由參照其全體內容而併入本說明書中。 本說明書所記載的全部文獻、專利申請案、及技術規格，均通過參考引用併入本說明書中，其程度與個別文獻、專利申請案、及技術規格而被具體併入本說明書的程度相同。 The contents disclosed in Japanese Patent Application No. 2022-045974 are incorporated into this specification by reference to the entire contents. All documents, patent applications, and technical specifications described in this specification are incorporated by reference into this specification to the same extent as if the individual documents, patent applications, and technical specifications were specifically incorporated into this specification.
圖1係實施例1所獲得接合體之截面的電子顯微鏡影像。 圖2係圖1所示電子顯微鏡影像的部分放大影像。 圖3係比較例1所獲得接合體之截面的電子顯微鏡影像。 圖4係圖3所示電子顯微鏡影像的部分放大影像。 Figure 1 is an electron microscope image of the cross-section of the bonded body obtained in Example 1. Figure 2 is a partially enlarged image of the electron microscope image shown in Figure 1. FIG. 3 is an electron microscope image of the cross-section of the bonded body obtained in Comparative Example 1. Figure 4 is a partially enlarged image of the electron microscope image shown in Figure 3.
Claims (9)
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| JP2022-045974 | 2022-03-22 | ||
| JP2022045974 | 2022-03-22 |
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| JPH01312893A (en) * | 1988-06-09 | 1989-12-18 | Fujitsu Ltd | Manufacture of printed board |
| JP5400826B2 (en) * | 2011-04-08 | 2014-01-29 | 三井金属鉱業株式会社 | Composite metal foil and manufacturing method thereof |
| JP5728118B1 (en) * | 2014-09-22 | 2015-06-03 | 株式会社Ｓｈカッパープロダクツ | Surface-treated copper foil, method for producing the surface-treated copper foil, and copper-clad laminate using the surface-treated copper foil |
| KR102394732B1 (en) * | 2018-04-27 | 2022-05-09 | 제이엑스금속주식회사 | Surface-treated copper foil, copper clad laminate and printed wiring board |
| KR20220119391A (en) * | 2019-12-26 | 2022-08-29 | 나믹스 가부시끼가이샤 | Composite copper member treated with silane coupling agent |
| WO2021193863A1 (en) * | 2020-03-27 | 2021-09-30 | 古河電気工業株式会社 | Surface-treated copper foil for printed wiring boards, and copper-cladded laminate board for printed wiring boards and printed wiring board each using same |
| JP7051988B1 (en) * | 2020-11-27 | 2022-04-11 | 古河電気工業株式会社 | Roughened copper foil, copper-clad laminate, and printed wiring board |
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