JP7398362B2 - Method for manufacturing laminate - Google Patents
Method for manufacturing laminate Download PDFInfo
- Publication number
- JP7398362B2 JP7398362B2 JP2020511109A JP2020511109A JP7398362B2 JP 7398362 B2 JP7398362 B2 JP 7398362B2 JP 2020511109 A JP2020511109 A JP 2020511109A JP 2020511109 A JP2020511109 A JP 2020511109A JP 7398362 B2 JP7398362 B2 JP 7398362B2
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- Prior art keywords
- metal
- acid
- base material
- metal base
- organic
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- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 238000000034 method Methods 0.000 title claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 179
- 239000002184 metal Substances 0.000 claims description 179
- 239000000463 material Substances 0.000 claims description 98
- 229910021645 metal ion Inorganic materials 0.000 claims description 57
- 239000013110 organic ligand Substances 0.000 claims description 35
- 239000000758 substrate Substances 0.000 claims description 34
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 21
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 21
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 16
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 14
- 239000012621 metal-organic framework Substances 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 9
- 230000003213 activating effect Effects 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 239000011976 maleic acid Substances 0.000 claims description 8
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 7
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims description 7
- SATWKVZGMWCXOJ-UHFFFAOYSA-N 4-[3,5-bis(4-carboxyphenyl)phenyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC(C=2C=CC(=CC=2)C(O)=O)=CC(C=2C=CC(=CC=2)C(O)=O)=C1 SATWKVZGMWCXOJ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- MPFLRYZEEAQMLQ-UHFFFAOYSA-N dinicotinic acid Chemical compound OC(=O)C1=CN=CC(C(O)=O)=C1 MPFLRYZEEAQMLQ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 150000003852 triazoles Chemical class 0.000 claims description 7
- KFSUCTRGHQKXSV-UHFFFAOYSA-N 5-(1h-pyrazol-5-yl)-1h-pyrazole Chemical compound N1N=CC=C1C1=CC=NN1 KFSUCTRGHQKXSV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910000599 Cr alloy Inorganic materials 0.000 claims description 5
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 56
- -1 poly(ethylene glycol) Polymers 0.000 description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000005530 etching Methods 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 125000000524 functional group Chemical group 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 125000000623 heterocyclic group Chemical group 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- 229920002266 Pluriol® Polymers 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- GJAWHXHKYYXBSV-UHFFFAOYSA-N quinolinic acid Chemical compound OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- IIQLVLWFQUUZII-UHFFFAOYSA-N 2-amino-5-(4-amino-3-carboxyphenyl)benzoic acid Chemical compound C1=C(C(O)=O)C(N)=CC=C1C1=CC=C(N)C(C(O)=O)=C1 IIQLVLWFQUUZII-UHFFFAOYSA-N 0.000 description 3
- SEILKFZTLVMHRR-UHFFFAOYSA-N 2-phosphonooxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(O)=O SEILKFZTLVMHRR-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 3
- 229910000071 diazene Inorganic materials 0.000 description 3
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 3
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- ZEVWQFWTGHFIDH-UHFFFAOYSA-N 1h-imidazole-4,5-dicarboxylic acid Chemical compound OC(=O)C=1N=CNC=1C(O)=O ZEVWQFWTGHFIDH-UHFFFAOYSA-N 0.000 description 2
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 2
- QNVNLUSHGRBCLO-UHFFFAOYSA-N 5-hydroxybenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC(O)=CC(C(O)=O)=C1 QNVNLUSHGRBCLO-UHFFFAOYSA-N 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
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 150000007824 aliphatic compounds Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 2
- VAMFXQBUQXONLZ-UHFFFAOYSA-N icos-1-ene Chemical compound CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- HRRDCWDFRIJIQZ-UHFFFAOYSA-N naphthalene-1,8-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=CC2=C1 HRRDCWDFRIJIQZ-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- ZUCRGHABDDWQPY-UHFFFAOYSA-N pyrazine-2,3-dicarboxylic acid Chemical compound OC(=O)C1=NC=CN=C1C(O)=O ZUCRGHABDDWQPY-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- MMXZSJMASHPLLR-UHFFFAOYSA-N pyrroloquinoline quinone Chemical compound C12=C(C(O)=O)C=C(C(O)=O)N=C2C(=O)C(=O)C2=C1NC(C(=O)O)=C2 MMXZSJMASHPLLR-UHFFFAOYSA-N 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 2
- KQTIIICEAUMSDG-UHFFFAOYSA-N tricarballylic acid Chemical compound OC(=O)CC(C(O)=O)CC(O)=O KQTIIICEAUMSDG-UHFFFAOYSA-N 0.000 description 2
- 150000003628 tricarboxylic acids Chemical class 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- TXXHDPDFNKHHGW-UHFFFAOYSA-N (2E,4E)-2,4-hexadienedioic acid Natural products OC(=O)C=CC=CC(O)=O TXXHDPDFNKHHGW-UHFFFAOYSA-N 0.000 description 1
- GGAUUQHSCNMCAU-ZXZARUISSA-N (2s,3r)-butane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C[C@H](C(O)=O)[C@H](C(O)=O)CC(O)=O GGAUUQHSCNMCAU-ZXZARUISSA-N 0.000 description 1
- OYUWHGGWLCJJNP-UHFFFAOYSA-N 1,2-Dihydrophthalic acid Chemical compound OC(=O)C1C=CC=CC1C(O)=O OYUWHGGWLCJJNP-UHFFFAOYSA-N 0.000 description 1
- QSMUFXXTSUEZJA-UHFFFAOYSA-N 1,3-dibenzyl-2-oxoimidazolidine-4,5-dicarboxylic acid Chemical compound O=C1N(CC=2C=CC=CC=2)C(C(=O)O)C(C(O)=O)N1CC1=CC=CC=C1 QSMUFXXTSUEZJA-UHFFFAOYSA-N 0.000 description 1
- HXAWZHYWALRESW-UHFFFAOYSA-N 1,4-bis(carboxymethyl)piperazine-2,3-dicarboxylic acid Chemical compound OC(=O)CN1CCN(CC(O)=O)C(C(O)=O)C1C(O)=O HXAWZHYWALRESW-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical group CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- DVGKVEDUHFAIMD-UHFFFAOYSA-N 1-amino-4-methyl-9,10-dioxoanthracene-2,3-dicarboxylic acid Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(N)=C(C(O)=O)C(C(O)=O)=C2C DVGKVEDUHFAIMD-UHFFFAOYSA-N 0.000 description 1
- JIDODOMERXIGRG-UHFFFAOYSA-N 1-benzylpyrrole-3,4-dicarboxylic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CN1CC1=CC=CC=C1 JIDODOMERXIGRG-UHFFFAOYSA-N 0.000 description 1
- XJDOBMJUQFBURS-UHFFFAOYSA-N 1-methylnonane-1,3,5,7-tetracarboxylic acid Chemical compound CCC(C(O)=O)CC(C(O)=O)CC(C(O)=O)CC(C)C(O)=O XJDOBMJUQFBURS-UHFFFAOYSA-N 0.000 description 1
- RHWLNSGYGAWNLU-UHFFFAOYSA-N 1-methylpyrrole-3,4-dicarboxylic acid Chemical compound CN1C=C(C(O)=O)C(C(O)=O)=C1 RHWLNSGYGAWNLU-UHFFFAOYSA-N 0.000 description 1
- PNKBWDYDQQBDSN-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalene-2,3-dicarboxylic acid Chemical compound C1=CC=C2C(C=3C4=CC=CC=C4C=C(C=3C(O)=O)C(=O)O)=CC=CC2=C1 PNKBWDYDQQBDSN-UHFFFAOYSA-N 0.000 description 1
- ZUUNZDIGHGJBAR-UHFFFAOYSA-N 1h-imidazole-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CNC(C(O)=O)=N1 ZUUNZDIGHGJBAR-UHFFFAOYSA-N 0.000 description 1
- YDMVPJZBYSWOOP-UHFFFAOYSA-N 1h-pyrazole-3,5-dicarboxylic acid Chemical compound OC(=O)C=1C=C(C(O)=O)NN=1 YDMVPJZBYSWOOP-UHFFFAOYSA-N 0.000 description 1
- IKTPUTARUKSCDG-UHFFFAOYSA-N 1h-pyrazole-4,5-dicarboxylic acid Chemical compound OC(=O)C=1C=NNC=1C(O)=O IKTPUTARUKSCDG-UHFFFAOYSA-N 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-N 2,2-diethylpropanedioic acid Chemical compound CCC(CC)(C(O)=O)C(O)=O LTMRRSWNXVJMBA-UHFFFAOYSA-N 0.000 description 1
- ZJQZWNLKRBUEKX-UHFFFAOYSA-N 2,5-dianilinoterephthalic acid Chemical compound OC(=O)C=1C=C(NC=2C=CC=CC=2)C(C(=O)O)=CC=1NC1=CC=CC=C1 ZJQZWNLKRBUEKX-UHFFFAOYSA-N 0.000 description 1
- KFZMASHKIDYKFD-UHFFFAOYSA-N 2-(2-ethoxyethoxymethyl)propanedioic acid Chemical compound CCOCCOCC(C(O)=O)C(O)=O KFZMASHKIDYKFD-UHFFFAOYSA-N 0.000 description 1
- CABMTIJINOIHOD-UHFFFAOYSA-N 2-[4-methyl-5-oxo-4-(propan-2-yl)-4,5-dihydro-1H-imidazol-2-yl]quinoline-3-carboxylic acid Chemical compound N1C(=O)C(C(C)C)(C)N=C1C1=NC2=CC=CC=C2C=C1C(O)=O CABMTIJINOIHOD-UHFFFAOYSA-N 0.000 description 1
- RTZDLIFCPWVQEZ-UHFFFAOYSA-N 2-benzoylbenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(=O)C1=CC=CC=C1 RTZDLIFCPWVQEZ-UHFFFAOYSA-N 0.000 description 1
- MVDKKZZVTWHVMC-UHFFFAOYSA-N 2-hexadecylpropanedioic acid Chemical compound CCCCCCCCCCCCCCCCC(C(O)=O)C(O)=O MVDKKZZVTWHVMC-UHFFFAOYSA-N 0.000 description 1
- HSBSUGYTMJWPAX-UHFFFAOYSA-N 2-hexenedioic acid Chemical compound OC(=O)CCC=CC(O)=O HSBSUGYTMJWPAX-UHFFFAOYSA-N 0.000 description 1
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- JPGZDTDZZDLVHW-UHFFFAOYSA-N quinoline-2,4-dicarboxylic acid Chemical compound C1=CC=CC2=NC(C(=O)O)=CC(C(O)=O)=C21 JPGZDTDZZDLVHW-UHFFFAOYSA-N 0.000 description 1
- SXXBQGWQCRMKHR-UHFFFAOYSA-N quinoline-3,4-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CN=C21 SXXBQGWQCRMKHR-UHFFFAOYSA-N 0.000 description 1
- WCHKKUMRGPRZOG-UHFFFAOYSA-N quinoline-7,8-dicarboxylic acid Chemical compound C1=CC=NC2=C(C(O)=O)C(C(=O)O)=CC=C21 WCHKKUMRGPRZOG-UHFFFAOYSA-N 0.000 description 1
- CQZDWYYGOZOTHY-UHFFFAOYSA-N quinoxaline-2,3-dicarboxylic acid Chemical compound C1=CC=C2N=C(C(O)=O)C(C(=O)O)=NC2=C1 CQZDWYYGOZOTHY-UHFFFAOYSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- ZWWLLYJRPKYTDF-UHFFFAOYSA-N thiophene-3,4-dicarboxylic acid Chemical compound OC(=O)C1=CSC=C1C(O)=O ZWWLLYJRPKYTDF-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 125000002088 tosyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])S(*)(=O)=O 0.000 description 1
- TXXHDPDFNKHHGW-ZPUQHVIOSA-N trans,trans-muconic acid Chemical compound OC(=O)\C=C\C=C\C(O)=O TXXHDPDFNKHHGW-ZPUQHVIOSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/26—Drying gases or vapours
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/26—Drying gases or vapours
- B01D53/28—Selection of materials for use as drying agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
-
- 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
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F13/00—Arrangements for modifying heat-transfer, e.g. increasing, decreasing
- F28F13/18—Arrangements for modifying heat-transfer, e.g. increasing, decreasing by applying coatings, e.g. radiation-absorbing, radiation-reflecting; by surface treatment, e.g. polishing
Description
本開示は、積層体の製造方法、および該製造方法により得られる積層体に関する。 The present disclosure relates to a method for producing a laminate, and a laminate obtained by the method.
金属有機構造体（ＭＯＦ：Metal Organic Framework）は、多孔質の配位ネットワーク構造を有し、吸着材、触媒等として用いられている。かかる金属有機構造体は、支持体の表面に形成され、積層体として用いられ得る。 A metal organic framework (MOF) has a porous coordination network structure and is used as an adsorbent, a catalyst, and the like. Such a metal-organic framework can be formed on the surface of a support and used as a laminate.
支持体とその表面に形成された金属有機構造体を含む積層体およびその製造方法は、例えば、特許文献１に記載されている。特許文献１では、（ａ）支持体表面の少なくとも一部の上に、少なくとも一種の金属イオンを含む第一の溶液を吹き付ける工程と、（ｂ）該支持体表面の少なくとも一部の上に、少なくとも二座の有機化合物の少なくとも一種を含む第二の溶液を吹き付ける工程とを含み、工程（ｂ）が、工程（ａ）の前で、後で、あるいは同時に行われて、多孔性金属有機構造体の層を形成する方法により、積層体が製造されている。 A laminate including a support and a metal-organic structure formed on the surface thereof and a method for manufacturing the same are described in, for example, Patent Document 1. Patent Document 1 discloses the following steps: (a) spraying a first solution containing at least one type of metal ion onto at least a portion of the surface of the support; (b) onto at least a portion of the surface of the support; spraying a second solution comprising at least one bidentate organic compound, step (b) being performed before, after, or simultaneously with step (a) to form a porous metal-organic structure. A laminate is manufactured by a method of forming body layers.
特許文献１に記載のような積層体は、支持体である基材の表面に重なった状態で金属有機構造体（以下、「ＭＯＦ」ともいう）が形成されている。本発明者らは、このような積層体においては、ＭＯＦ層は基材への密着性が低く、ＭＯＦ層が基材から剥離する不具合が生じ得ることを見出した。 In the laminate described in Patent Document 1, a metal-organic framework (hereinafter also referred to as "MOF") is formed so as to overlap the surface of a base material that is a support. The present inventors have found that in such a laminate, the MOF layer has low adhesion to the base material, and a problem may occur in which the MOF layer peels off from the base material.
本開示における課題は、金属有機構造体の剥離が抑制された金属基材とその上に形成された金属有機構造体とを有してなる積層体を提供することにある。 An object of the present disclosure is to provide a laminate including a metal base material in which peeling of the metal-organic structure is suppressed and a metal-organic structure formed thereon.
本開示は、以下の態様を含む。
１． 金属基材とその上に形成された金属有機構造体とを有してなる積層体の製造方法であって、
（工程１ａ）金属基材の表面を活性化する工程、または
（工程１ｂ）金属基材の表面を修飾し、その上に金属層を形成する工程、および
（工程２）上記工程１ａまたは工程１ｂで処理された金属基材を、少なくとも１種の金属イオンを含む溶液および少なくとも１種の有機配位子を含む溶液と接触させ、金属基材上に金属有機構造体を形成する工程
を含む製造方法。
２． 金属基材とその上に形成された金属有機構造体とを有してなる積層体の製造方法であって、
（工程１ａ）金属基材の表面を活性化する工程、および
（工程２）上記金属基材の表面を、少なくとも１種の金属イオンを含む溶液および少なくとも１種の有機配位子を含む溶液と接触させ、金属基材上に金属有機構造体を形成する工程
を含む製造方法。
３． 前記金属基材を構成する金属は、Ｓｉ、Ａｌ、Ｃｕ、Ｆｅ、Ｎｉ、もしくはＺｎ、またはＦｅ／Ｎｉ／Ｃｒ合金である、上記［１］または［２］に記載の製造方法。
４． 前記金属基材の表面を活性化する工程は、金属基材の表面を、フッ化水素、塩化水素、フッ素、または塩素で処理することにより行われる、上記［１］～［３］のいずれか１つに記載の製造方法。
５． 前記工程２において、溶液に含まれる金属イオンは、Ａｌ、Ｃｕ、Ｆｅ、Ｍｎ、またはＣｏのイオンである、上記［１］～［４］のいずれか１つに記載の製造方法。
６． 前記金属基材の表面に形成された金属イオンと、前記溶液中の金属イオンが同じである、上記［１］～［５］のいずれか１つに記載の製造方法。
７． 前記有機配位子は、１，４－ベンゼンジカルボン酸、１，２－ベンゼンジカルボン酸、マレイン酸、１，３，５－ベンゼントリカルボン酸、４，４’，４”－（１，３，５－ベンゼントリイル）トリス安息香酸、４，４’－ビピリジン、トリアゾール、イミダゾール、３，３’－ビピラゾール、ベンゾイミダゾール、および３，５－ピリジンジカルボン酸から選択される、上記［１］～［６］のいずれか１つに記載の製造方法。
８． 上記［１］～［７］のいずれか１つに記載の製造方法により得られる積層体。
９． 金属基材と該金属基材上に形成された金属有機構造体とを有してなる積層体であって、上記金属基材の表面の金属原子が、上記金属有機構造体の一部を構成している、積層体。
１０． 金属基材と該金属基材上に形成された金属有機構造体とを有してなる積層体であって、上記金属基材の表面が修飾されており、該修飾された表面上に金属層を有し、該金属層上に金属有機構造体が形成されている、積層体。
１１． 上記［９］または［１０］に記載の積層体から構成されるフィン。
１２． 上記［１１］に記載のフィンを有してなる、除加湿器。
１３． 上記［１１］に記載のフィンを有してなる、熱交換器。The present disclosure includes the following aspects.
1. A method for producing a laminate comprising a metal base material and a metal organic structure formed thereon, the method comprising:
(Step 1a) Activating the surface of the metal base material, or (Step 1b) modifying the surface of the metal base material and forming a metal layer thereon, and (Step 2) the above step 1a or step 1b. contacting a metal substrate treated with a solution containing at least one metal ion and a solution containing at least one organic ligand to form a metal-organic framework on the metal substrate. Method.
2. A method for producing a laminate comprising a metal base material and a metal organic structure formed thereon, the method comprising:
(Step 1a) Activating the surface of the metal substrate; and (Step 2) treating the surface of the metal substrate with a solution containing at least one metal ion and at least one organic ligand. A manufacturing method comprising the step of contacting to form a metal-organic structure on a metal substrate.
3. The manufacturing method according to [1] or [2] above, wherein the metal constituting the metal base material is Si, Al, Cu, Fe, Ni, or Zn, or a Fe/Ni/Cr alloy.
4. Any one of [1] to [3] above, wherein the step of activating the surface of the metal base material is performed by treating the surface of the metal base material with hydrogen fluoride, hydrogen chloride, fluorine, or chlorine. 1. The manufacturing method according to item 1.
5. The manufacturing method according to any one of [1] to [4] above, wherein in the step 2, the metal ions contained in the solution are Al, Cu, Fe, Mn, or Co ions.
6. The manufacturing method according to any one of [1] to [5] above, wherein the metal ions formed on the surface of the metal base material and the metal ions in the solution are the same.
7. The organic ligands include 1,4-benzenedicarboxylic acid, 1,2-benzenedicarboxylic acid, maleic acid, 1,3,5-benzenedicarboxylic acid, 4,4',4''-(1,3,5 -benzentriyl)trisbenzoic acid, 4,4'-bipyridine, triazole, imidazole, 3,3'-bipyrazole, benzimidazole, and 3,5-pyridinedicarboxylic acid, [1] to [6] above. ] The manufacturing method according to any one of the above.
8. A laminate obtained by the manufacturing method according to any one of [1] to [7] above.
9. A laminate comprising a metal base material and a metal organic structure formed on the metal base material, wherein metal atoms on the surface of the metal base constitute a part of the metal organic structure. It is a laminate.
10. A laminate comprising a metal base material and a metal organic structure formed on the metal base material, the surface of the metal base material being modified, and a metal layer on the modified surface. A laminate comprising: a metal organic structure formed on the metal layer.
11. A fin comprising the laminate according to [9] or [10] above.
12. A dehumidifier comprising the fin according to [11] above.
13. A heat exchanger comprising the fins according to [11] above.
本開示によれば、金属基材とその上に形成された金属有機構造体とを有してなる積層体において、金属有機構造体が基材から剥がれることを抑制することができる。 According to the present disclosure, in a laminate including a metal base material and a metal organic structure formed thereon, it is possible to suppress peeling of the metal organic structure from the base material.
以下、本開示の製造方法について説明する。 The manufacturing method of the present disclosure will be described below.
本開示の製造方法は、金属基材とその上に形成された金属有機構造体とを有してなる積層体の製造方法であって、
（工程１ａ）金属基材の表面を活性化する工程、
（工程１ｂ）金属基材の表面を修飾し、その上に金属層を形成する工程、および
（工程２）上記工程１ａまたは工程１ｂで処理された金属基材を、少なくとも１種の金属イオンを含む溶液および少なくとも１種の有機配位子を含む溶液と接触させ、金属基材上に金属有機構造体を形成する工程
を含む。The manufacturing method of the present disclosure is a method of manufacturing a laminate including a metal base material and a metal organic structure formed thereon, comprising:
(Step 1a) activating the surface of the metal base material,
(Step 1b) A step of modifying the surface of the metal base material and forming a metal layer thereon, and (Step 2) A step of modifying the surface of the metal base material and forming a metal layer thereon. and a solution containing at least one organic ligand to form a metal-organic framework on the metal substrate.
以下、工程１ａについて説明する。 Hereinafter, step 1a will be explained.
工程１ａは、金属基材の表面を活性化する工程である。 Step 1a is a step of activating the surface of the metal base material.
まず、金属基材を準備する。 First, a metal base material is prepared.
上記金属基材を構成する金属は、Ｓｉ、Ａｌ、Ｃｕ、Ｆｅ、Ｎｉ、もしくはＺｎ、またはこれらを含む合金であり得る。 The metal constituting the metal base material may be Si, Al, Cu, Fe, Ni, or Zn, or an alloy containing these.
上記合金としては、特に限定されないが、例えばＦｅ／Ｎｉ／Ｃｒ合金、Ａｌ／Ｃｕ合金等が挙げられる。 The above-mentioned alloy is not particularly limited, but includes, for example, Fe/Ni/Cr alloy, Al/Cu alloy, and the like.
好ましい態様において、金属基材を構成する金属は、Ａｌである。 In a preferred embodiment, the metal constituting the metal base material is Al.
上記金属基材の形状は、特に限定されず、用途に応じて種々の形状であり得る。下記するように、本開示の積層体は、ＭＯＦ層の剥離が生じにくいので、複雑な形状の基材であっても使用することができる。例えば、上記金属基材の形状は、板状、棒状などの単純な形状に加え、表面積を大きくするための、フィン状、凹凸形状、細孔構造等であってもよい。表面積を大きくし、ＭＯＦの機能を最大限に利用できることから、フィン状、凹凸形状、細孔構造等が好ましい。 The shape of the metal base material is not particularly limited, and may have various shapes depending on the purpose. As described below, the laminate of the present disclosure is less likely to cause peeling of the MOF layer, so it can be used even with a base material having a complicated shape. For example, the shape of the metal base material may be a simple shape such as a plate shape or a rod shape, or may be a fin shape, an uneven shape, a pore structure, etc. in order to increase the surface area. A fin shape, an uneven shape, a pore structure, etc. are preferable because the surface area can be increased and the functions of the MOF can be utilized to the maximum.
次に、上記金属基材の表面を処理することにより、金属基材の表面を活性化する。 Next, the surface of the metal base material is activated by treating the surface of the metal base material.
上記処理は、金属基材の表面を活性化できる処理であれば特に限定されないが、例えばエッチング、Ｏ２イオン処理、大気圧プラズマ処理、ＵＶＯ３（紫外線－オゾン）処理、熱水処理等が挙げられる。好ましくは、エッチング処理が用いられる。The above treatment is not particularly limited as long as it can activate the surface of the metal base material, but examples include etching, O 2 ion treatment, atmospheric pressure plasma treatment, UVO 3 (ultraviolet ozone) treatment, hot water treatment, etc. It will be done. Preferably, an etching process is used.
上記活性化とは、下記する工程２の処理により有機配位子が金属基材の表面と結合し、金属有機構造体を形成できる状態をいう。例えば、金属基材の表面の活性化は、金属基材の表面に金属イオンを形成することを含む。 The above-mentioned activation refers to a state in which the organic ligand is bonded to the surface of the metal base material by the treatment in Step 2 described below, and a metal-organic structure can be formed. For example, activating the surface of a metal substrate includes forming metal ions on the surface of the metal substrate.
上記エッチングは、上記金属基材の表面を、金属基材の種類に応じて、フッ化水素、塩化水素、フッ素、または塩素等のエッチング剤で処理することにより行うことができる。中でも、溶液として扱えることからフッ化水素によるエッチングが好ましい。 The etching can be performed by treating the surface of the metal base material with an etching agent such as hydrogen fluoride, hydrogen chloride, fluorine, or chlorine depending on the type of the metal base material. Among these, etching using hydrogen fluoride is preferable because it can be treated as a solution.
上記金属基材の表面のエッチング剤での処理は、金属基材の表面とエッチング剤とを接触させることにより行うことができる。処理に用いるエッチング剤は、気体であっても、液体であってもよいが、好ましくは液体である。 The treatment of the surface of the metal base material with the etching agent can be performed by bringing the surface of the metal base material into contact with the etching agent. The etching agent used in the treatment may be a gas or a liquid, but is preferably a liquid.
上記エッチング剤での処理温度は、好ましくは０～５０℃、より好ましくは１０～３０℃、典型的には室温である。 The treatment temperature with the above etching agent is preferably 0 to 50°C, more preferably 10 to 30°C, and typically room temperature.
上記エッチング剤での処理時間は、好ましくは３０～６０分、より好ましくは１５～３０分である。 The treatment time with the above etching agent is preferably 30 to 60 minutes, more preferably 15 to 30 minutes.
次に、工程１ｂについて説明する。 Next, step 1b will be explained.
工程１ｂは、金属基材の表面を修飾し、その上に金属層を形成する工程である。 Step 1b is a step of modifying the surface of the metal base material and forming a metal layer thereon.
まず、工程１ａと同様に金属基材を準備する。 First, a metal base material is prepared in the same manner as in step 1a.
次いで、上記金属基材の表面を処理して、表面を修飾する。 Next, the surface of the metal base material is treated to modify the surface.
ここに、「修飾する」とは、金属基材の表面に、官能基または分子を付与し、表面を改質することを意味する。 Here, "modifying" means adding a functional group or molecule to the surface of a metal base material to modify the surface.
上記金属基材の表面を修飾する方法としては、例えば、金属基材の表面に付与したい化合物、例えばポリ（エチレングリコール）メタクリレート等を、金属基材の表面とのカップリング能を有する化合物、例えばメタクリロイルオキシエチルフォスフェート等と共重合させ、得られた共重合体で金属基材の表面を処理することにより行うことができる。 As a method for modifying the surface of the metal base material, for example, a compound to be added to the surface of the metal base material, such as poly(ethylene glycol) methacrylate, and a compound having a coupling ability with the surface of the metal base material, such as This can be carried out by copolymerizing with methacryloyloxyethyl phosphate or the like and treating the surface of a metal substrate with the obtained copolymer.
好ましい態様において、上記共重合体としては、ポリ（エチレングリコール）メタクリレート／メタクリロイルオキシエチルフォスフェート共重合体（重合比は、９９／１～８０／２０、好ましくは９９／１～９５／５、具体的には９７／３である）等が挙げられる。 In a preferred embodiment, the copolymer is poly(ethylene glycol) methacrylate/methacryloyloxyethyl phosphate copolymer (polymerization ratio is 99/1 to 80/20, preferably 99/1 to 95/5, specifically In particular, it is 97/3).
上記処理により、共重合体は、そのカップリング能を有する部分（メタクリロイルオキシエチルフォスフェート由来の部分）により金属基材と結合し、金属基材の表面を修飾する。 Through the above treatment, the copolymer binds to the metal substrate through its coupling-capable portion (the portion derived from methacryloyloxyethyl phosphate), thereby modifying the surface of the metal substrate.
次いで、表面が修飾された金属基材を処理して、金属基材の修飾面に金属層を形成する。かかる処理の方法としては、上記で修飾された金属基材を、金属イオンを含む処理剤、例えば金属アルコキシドのアルコール溶液で処理することにより行うことができる。 The surface-modified metal substrate is then treated to form a metal layer on the modified surface of the metal substrate. Such treatment can be carried out by treating the metal base material modified above with a treatment agent containing metal ions, for example, an alcoholic solution of metal alkoxide.
例えば、修飾された金属基材上にＡｌ層を形成する場合には、アルミニウムブトキシドのエタノール溶液で処理する。 For example, when forming an Al layer on a modified metal substrate, it is treated with an ethanol solution of aluminum butoxide.
上記工程１ａまたは工程１ｂにおいて処理された金属基材を工程２に付す。以下、工程２について説明する。 The metal base material treated in the above step 1a or step 1b is subjected to step 2. Step 2 will be explained below.
工程２は、上記で処理された金属基材の表面を、少なくとも１種の金属イオンを含む溶液および少なくとも１種の有機配位子を含む溶液と接触させ、金属基材上に金属有機構造体を形成する工程である。 Step 2 is to contact the surface of the metal substrate treated above with a solution containing at least one type of metal ion and a solution containing at least one type of organic ligand to form a metal-organic structure on the metal substrate. This is the process of forming.
上記溶液に含まれる金属イオンは、特に限定されないが、例えば、Ｉａ族、ＩＩａ族、ＩＩＩａ族、ＩＶａ～ＶＩＩＩ族、Ｉｂ～ＶＩｂ族からなる群から選択される金属のイオンである。かかる金属イオンは、好ましくは、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｓｃ、Ｙ、Ｔｉ、Ｚｒ、Ｈｆ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｗ、Ｍｎ、Ｒｅ、Ｆｅ、Ｒｏ、Ｏｓ、Ｃｏ、Ｒｈ、Ｉｒ、Ｎｉ、Ｐｄ、Ｐｔ、Ｃｕ、Ａｇ、Ａｕ、Ｚｎ、Ｃｄ、Ｈｇ、Ａｌ、Ｇａ、Ｉｎ、ＴＩ、Ｓｉ、Ｇｅ、Ｓｎ、Ｐｂ、Ａｓ、Ｓｂ、Ｂｉ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｐｍ、Ｓｍ、Ｅｎ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、およびＹｂのイオンであり得る。 The metal ions contained in the solution are not particularly limited, but are, for example, metal ions selected from the group consisting of Group Ia, Group IIa, Group IIIa, Groups IVa to VIII, and Groups Ib to VIb. Such metal ions are preferably Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ro, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, TI, Si, Ge, Sn, Pb, As, Sb, Bi, La, Ce, Pr, The ions can be Nd, Pm, Sm, En, Gd, Tb, Dy, Ho, Er, Tm, and Yb.
具体的には、かかる金属イオンは、Ｍｇ２＋、Ｃａ２＋、Ｓｒ２＋、Ｂａ２＋、Ｓｃ３＋、Ｙ３＋、Ｌｎ３＋、Ｔｉ４＋、Ｚｒ４＋、Ｈｆ４＋、Ｖ４＋、Ｖ３＋、Ｖ２＋、Ｎｂ３＋、Ｔａ３＋、Ｃｒ３＋、Ｍｏ３＋、Ｗ３＋、Ｍｎ３＋、Ｍｎ２＋、Ｒｅ３＋、Ｒｅ２＋、Ｆｅ３＋、Ｆｅ２＋、Ｒｕ３＋、Ｒｕ２＋、Ｏｓ３＋、Ｏｓ２＋、Ｃｏ３＋、Ｃｏ２＋、Ｒｈ２＋、Ｒｈ＋、Ｉｒ２＋、Ｉｒ＋、Ｎｉ２＋、Ｎｉ＋、Ｐｄ２＋、Ｐｄ＋、Ｐｔ２＋、Ｐｔ＋、Ｃｕ２＋、Ｃｕ＋、Ａｇ＋、Ａｕ＋、Ｚｎ２＋、Ｃｄ２＋、Ｈｇ２＋、Ａｌ３＋、Ｇａ３＋、ｌｎ３＋、ＴＩ３＋、Ｓｉ４＋、Ｓｉ２＋、Ｇｅ４＋、Ｇｅ２＋、Ｓｎ４＋、Ｓｎ２＋、Ｐｂ４＋、Ｐｂ２＋、Ａｓ５＋、Ａｓ３＋、Ａｓ＋、Ｓｂ５＋、Ｓｂ３＋、Ｓｂ＋、Ｂｉ５＋、Ｂｉ３＋、Ｂｉ＋、Ｌａ３＋、Ｃｅ３＋、Ｐｒ３＋、Ｎｄ３＋、Ｐｍ３＋、Ｓｍ３＋、Ｅｎ３＋、Ｇｄ３＋、Ｔｂ３＋、Ｄｙ３＋、Ｈｏ３＋、Ｅｒ３＋、Ｔｍ３＋、またはＹｂ３＋であり得る。Specifically, such metal ions include Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Sc 3+ , Y 3+ , Ln 3+ , Ti 4+ , Zr 4+ , Hf 4+ , V 4+ , V 3+ , V 2+ , Nb 3+ , Ta 3+ , Cr 3+ , Mo 3+ , W 3+ , Mn 3+ , Mn 2+ , Re 3+ , Re 2+ , Fe 3+ , Fe 2+ , Ru 3+ , Ru 2+ , Os 3+ , Os 2+ , Co 3+ , Co 2+ , Rh 2+ , Rh + , Ir 2+ , Ir + , Ni 2+ , Ni + , Pd 2+ , Pd + , Pt 2+ , Pt + , Cu 2+ , Cu + , Ag + , Au + , Zn 2+ , Cd 2+ , Hg 2+ , Al 3+ , Ga 3+ , ln 3+ , TI 3+ , Si 4+ , Si 2+ , Ge 4+ , Ge 2+ , Sn 4+ , Sn 2+ , Pb 4+ , Pb 2+ , As 5+ , As 3+ , As + , Sb 5+ , Sb 3+ , Sb + , Bi 5+ , Bi 3+ , Bi + , La 3+ , Ce 3+ , Pr 3+ , Nd 3+ , Pm 3+ , Sm 3+ , En 3+ , Gd 3+ , Tb 3+ , Dy 3+ , Ho 3+ , Er 3+ , It can be Tm 3+ or Yb 3+ .
上記金属イオンは、１種のみであっても２種以上であってもよい。好ましくは、上記金属イオンは１種である。 The number of the above-mentioned metal ions may be one type or two or more types. Preferably, the number of metal ions is one.
好ましい態様において、上記金属イオンは、Ａｌ３＋、Ｃｕ２＋、Ｃｕ＋、Ｆｅ３＋、Ｆｅ２＋、Ｍｎ３＋、Ｍｎ２＋、Ｃｏ３＋、またはＣｏ２＋であり、好ましくはＡｌ３＋、Ｆｅ３＋である。In a preferred embodiment, the metal ion is Al 3+ , Cu 2+ , Cu + , Fe 3+ , Fe 2+ , Mn 3+ , Mn 2+ , Co 3+ , or Co 2+ , preferably Al 3+ , Fe 3+ .
上記溶液に含まれる金属イオンは、上記金属基材の表面に形成される金属イオンと同じであっても、異なっていてもよいが、好ましくは同じである。 The metal ions contained in the solution may be the same as or different from the metal ions formed on the surface of the metal base material, but preferably they are the same.
上記金属イオンを含む溶液は、上記金属イオンを含む塩の溶液であり得る。かかる塩は、有機酸塩、無機酸塩、有機塩基塩または無機塩基塩のいずれであってもよい。上記塩は、好ましくは無機酸塩である。 The solution containing the metal ion may be a solution of a salt containing the metal ion. Such salts may be organic acid salts, inorganic acid salts, organic base salts or inorganic base salts. The above salt is preferably an inorganic acid salt.
上記有機酸塩としては、例えば、モノカルボン酸塩（例えば、酢酸塩、トリフルオロ酢酸塩、酪酸塩、パルミチン酸塩、ステアリン酸塩など）、多価カルボン酸塩（例えば、フマル酸塩、マレイン酸塩など）、オキシカルボン酸塩（例えば、乳酸塩、酒石酸塩、クエン酸塩、コハク酸塩、マロン酸塩など）、有機スルホン酸塩（例えば、メタンスルホン酸塩、トルエンスルホン酸塩、トシル酸塩など）等が挙げられる。 Examples of the above-mentioned organic acid salts include monocarboxylate salts (e.g., acetate, trifluoroacetate, butyrate, palmitate, stearate, etc.), polycarboxylate salts (e.g., fumarate, maleate, etc.). salts), oxycarboxylate salts (e.g. lactate, tartrate, citrate, succinate, malonate, etc.), organic sulfonates (e.g. methanesulfonate, toluenesulfonate, tosyl salts, etc.).
上記無機酸塩としては、例えば、塩酸塩、硫酸塩、硝酸塩、臭化水素酸塩、リン酸塩等が挙げられる。 Examples of the above-mentioned inorganic acid salts include hydrochlorides, sulfates, nitrates, hydrobromides, phosphates, and the like.
好ましい態様において、金属イオンを含む塩は、無機酸塩、特に硝酸塩であり得る。 In a preferred embodiment, the metal ion-containing salt may be an inorganic acid salt, especially a nitrate.
上記金属イオンを含む溶液の溶媒は、例えば、エタノール、ジメチルホルムアミド、トルエン、メタノール、クロロベンゼン、ジエチルホルムアミド、ジメチルスルホキシド、水、過酸化水素、メチルアミン、水酸化ナトリウム溶液、Ｎ－メチルピロリドンエーテル、アセトニトリル、塩化ベンジル、トリエチルアミン、もしくはエチレングリコール、またはこれらの混合物であり得る。 Examples of solvents for the solution containing the metal ions include ethanol, dimethylformamide, toluene, methanol, chlorobenzene, diethylformamide, dimethyl sulfoxide, water, hydrogen peroxide, methylamine, sodium hydroxide solution, N-methylpyrrolidone ether, and acetonitrile. , benzyl chloride, triethylamine, or ethylene glycol, or mixtures thereof.
上記金属イオンを含む溶液は、好ましくは５～２０質量％、より好ましくは５～１０質量％であり得る。 The solution containing the metal ions may preferably have a concentration of 5 to 20% by weight, more preferably 5 to 10% by weight.
上記金属イオンを含む溶液は、他の成分として、触媒、酸等を含んでいてもよい。 The solution containing metal ions may also contain a catalyst, an acid, etc. as other components.
上記有機配位子は、上記金属基材の表面または金属層の表面の金属イオンおよび上記溶液に含まれる金属イオンと、少なくとも２つの配位結合を形成することができるものであれば特に限定されない。 The organic ligand is not particularly limited as long as it can form at least two coordination bonds with the metal ion on the surface of the metal base material or the surface of the metal layer and the metal ion contained in the solution. .
上記配位結合は、例えば、金属イオンと少なくとも１つの配位結合を形成することができる官能基により形成される。 The coordination bond is formed by, for example, a functional group that can form at least one coordination bond with a metal ion.
上記配位結合を形成することができる官能基としては、例えば、－ＣＯＯＨ、－ＣＳ２Ｈ、－ＮＯ２、－Ｂ（ＯＨ）２、－ＳＯ３Ｈ、－Ｓｉ（ＯＨ）３、－Ｇｅ（ＯＨ）３、－Ｓｎ（ＯＨ）３、－Ｓｉ（ＳＨ）４、－Ｇｅ（ＳＨ）４、－Ｓｎ（ＳＨ）３、－ＰＯ３Ｈ、－ＡｓＯ３Ｈ、－ＡｓＯ４Ｈ、－Ｐ（ＳＨ）３、－Ａｓ（ＳＨ）３、－ＣＨ（ＲＳＨ）２、－Ｃ（ＲＳＨ）３、－ＣＨ（ＲＮＨ２）２、－Ｃ（ＲＮＨ２）３、－ＣＨ（ＲＯＨ）２、－Ｃ（ＲＯＨ）３、－ＣＨ（ＲＣＮ）３、および－Ｃ（ＲＣＮ）３が挙げられる。上記式中、Ｒは、単結合、炭素数１～５のアルキレン基（例えば、メチレン、エチレン、ｎ－プロピレン、ｉ－プロピレン、ｎ－ブチレン、ｉ－ブチレン、ｔｅｒｔ－ブチレンまたはｎ－ペンチレン基）、炭素数６～１４の２価の芳香族基（例えば、例えばフェニレン）、または上記アルキレン基と芳香族基の組み合わせ（例えば、－フェニレン－アルキレン－フェニレン－）である。また、上記配位結合を形成することができる官能基としては、複素環中に含まれるヘテロ原子、好ましくは窒素原子であってもよい。Examples of the functional groups capable of forming the coordinate bond include -COOH, -CS 2 H, -NO 2 , -B(OH) 2 , -SO 3 H, -Si(OH) 3 , -Ge (OH) 3 , -Sn(OH) 3 , -Si(SH) 4 , -Ge(SH) 4 , -Sn(SH) 3 , -PO 3 H, -AsO 3 H, -AsO 4 H, -P (SH) 3 , -As(SH) 3 , -CH(RSH) 2 , -C(RSH) 3 , -CH(RNH 2 ) 2 , -C(RNH 2 ) 3 , -CH(ROH) 2 , - Examples include C(ROH) 3 , -CH(RCN) 3 , and -C(RCN) 3 . In the above formula, R is a single bond or an alkylene group having 1 to 5 carbon atoms (for example, methylene, ethylene, n-propylene, i-propylene, n-butylene, i-butylene, tert-butylene or n-pentylene group) , a divalent aromatic group having 6 to 14 carbon atoms (for example, phenylene), or a combination of the above alkylene group and an aromatic group (for example, -phenylene-alkylene-phenylene-). Further, the functional group capable of forming the coordinate bond may be a heteroatom contained in the heterocycle, preferably a nitrogen atom.
好ましい態様において、上記配位結合を形成することができる官能基は、－ＣＯＯＨ、－ＮＯ２等であり得る。In a preferred embodiment, the functional group capable of forming the coordinate bond may be -COOH, -NO 2 or the like.
上記有機配位子は、好ましくは、二座以上となるように上記官能基を有する。かかる有機配位子において、官能基以外の部分は、有機配位子が金属イオンと配位結合を形成できる限り、限定されない。 The organic ligand preferably has the functional group so as to be bidentate or more. In such an organic ligand, the parts other than the functional group are not limited as long as the organic ligand can form a coordinate bond with a metal ion.
一の態様において、上記有機配位子は、飽和もしくは不飽和の脂肪族化合物、芳香族化合物または脂肪族芳香族化合物に由来する。 In one embodiment, the organic ligand is derived from a saturated or unsaturated aliphatic, aromatic or aliphatic aromatic compound.
上記脂肪族化合物または脂肪族芳香族化合物の脂肪族部分は、直鎖、分枝鎖、または環状であってもよい。脂肪族部分は、環状である場合、複数の環を有していてもよい。上記脂肪族化合物または脂肪族芳香族化合物の脂肪族部分は、好ましくは１～１５個の炭素原子を有し、より好ましくは１～１０個の炭素原子、例えば１、２、３、４、５、６、７、８、９または１０個の炭素原子を有する。好ましい態様において、上記脂肪族部分は、メタン、アダマンタン、アセチレン、エチレンまたはブタジエンに由来する。 The aliphatic portion of the aliphatic compound or aliphatic aromatic compound may be linear, branched, or cyclic. When the aliphatic moiety is cyclic, it may have multiple rings. The aliphatic moiety of the aliphatic compound or aliphatic aromatic compound preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, such as 1, 2, 3, 4, 5 , 6, 7, 8, 9 or 10 carbon atoms. In a preferred embodiment, the aliphatic moiety is derived from methane, adamantane, acetylene, ethylene or butadiene.
上記芳香族化合物または脂肪族芳香族化合物の芳香族部分は、１個以上の環、例えば２、３、４または５個の環を有していてもよい。これらの環は、縮合していても、縮合していなくてもよい。上記芳香族化合物または脂肪族芳香族化合物の芳香族部分は、好ましくは１、２、または３個、より好ましくは１または２個の環を有する。また、上記化合物の各環は、環中に少なくとも１種のヘテロ原子、例えばＮ、Ｏ、Ｓ、Ｂ、Ｐ、Ｓｉ、Ａｌ、好ましくはＮ、ＯまたはＳを有していてもよい。芳香族化合物または脂肪族芳香族化合物の芳香族部分は、炭素数６の環を１または２個含むことが好ましい。芳香族部分は、２個である場合、かかる２個の環は縮合していても、縮合していなくてもよい。好ましい態様において、かかる芳香族部分は、ベンゼン、ナフタレン、ビフェニル、ビピリジルまたはピリジルに由来する。 The aromatic moiety of the aromatic compound or aliphatic aromatic compound may have one or more rings, for example 2, 3, 4 or 5 rings. These rings may be fused or unfused. The aromatic moiety of the aromatic compound or aliphatic aromatic compound preferably has 1, 2 or 3 rings, more preferably 1 or 2 rings. Each ring of the above compounds may also have at least one heteroatom in the ring, such as N, O, S, B, P, Si, Al, preferably N, O or S. The aromatic compound or the aromatic moiety of the aliphatic aromatic compound preferably contains one or two rings each having 6 carbon atoms. When there are two aromatic moieties, the two rings may or may not be fused. In preferred embodiments, such aromatic moieties are derived from benzene, naphthalene, biphenyl, bipyridyl or pyridyl.
一の態様において、上記有機配位子は、ジカルボン酸、トリカルボン酸またはテトラカルボン酸に由来する。 In one embodiment, the organic ligand is derived from dicarboxylic, tricarboxylic or tetracarboxylic acids.
上記ジカルボン酸としては、例えば、シュウ酸、コハク酸、酒石酸、マレイン酸、１，４－ブタンジカルボン酸、１，４－ブテンジカルボン酸、４－オキソピラン－２，６－ジカルボン酸、１，６－ヘキサンジカルボン酸、デカンジカルボン酸、１，８－ヘプタデカンジカルボン酸、１，９－ヘプタデカンジカルボン酸、ヘプタデカンジカルボン酸、アセチレンジカルボン酸、１，２－ベンゼンジカルボン酸、１，３－ベンゼンジカルボン酸、２，３－ピリジンジカルボン酸、ピリジン－２，３－ジカルボン酸、１，３－ブタジエン－１，４－ジカルボン酸、１，４－ベンゼンジカルボン酸、ｐ－ベンゼンジカルボン酸、イミダゾール－２，４－ジカルボン酸、２－メチルキノリン－３，４－ジカルボン酸、キノリン－２，４－ジカルボン酸、キノキサリン－２，３－ジカルボン酸、６－クロロキノキサリン－２，３－ジカルボン酸、４，４’－ジアミノフェニルメタン－３，３’－ジカルボン酸、キノリン－３，４－ジカルボン酸、７－クロロ－４－ヒドロキシキノリン－２，８－ジカルボン酸、ジイミドジカルボン酸、ピリジン－２，６－ジカルボン酸、２－メチルイミダゾール－４，５－ジカルボン酸、チオフェン－３，４－ジカルボン酸、２－イソプロピルイミダゾール－４，５－ジカルボン酸、テトラハイドロピラン－４，４－ジカルボン酸、ペリレン－３，９－ジカルボン酸、ペリレンジカルボン酸、プルリオールＥ２００－ジカルボン酸、３，６－ジオキサオクタンジカルボン酸、３，５－シクロヘキサジエン－１，２－ジカルボン酸、オクタンジカルボン酸、ペンタン－３，３－ジカルボン酸、４，４’－ジアミノ－１，１’－ビフェニル－３，３’－ジカルボン酸、４，４’－ジアミノビフェニル－３，３’－ジカルボン酸、ベンジジン－３，３’－ジカルボン酸、１，４－ビス（フェニルアミノ）ベンゼン－２，５－ジカルボン酸、１，１’－ビナフチルジカルボン酸、７－クロロ－８－メチルキノリン－２，３－ジカルボン酸、１－アニリノ－アントラキノン－２，４’－ジカルボン酸、ポリテトラヒドロフラン２５０－ジカルボン酸、１，４－ビス（カルボキシメチル）ピペラジン－２，３－ジカルボン酸、７－クロロキノリン－３，８－ジカルボン酸、１－（４－カルボキシ）フェニル－３－（４－クロロ）フェニルピラゾリン－４，５－ジカルボン酸、１，４，５，６，７，７－ヘキサクロロ－５－ノルボルネン－２，３－ジカルボン酸、フェニルインダンジカルボン酸、１，３－ジベンジル－２－オキソイミダゾリジン－４，５－ジカルボン酸、１，４－シクロヘキサンジカルボン酸、ナフタレン－１，８－ジカルボン酸、２－ベンゾイルベンゼン－１，３－ジカルボン酸、１，３－ジベンジル－２－オキソイミダゾリデン－４，５－ｃｉｓ－ジカルボン酸、２，２’－ビキノリン－４，４’－ジカルボン酸、ピリジン－３，４－ジカルボン酸、３，６，９－トリオキサウンデカンジカルボン酸、ヒドロキシベンゾフェノンジカルボン酸、プルリオールＥ３００－ジカルボン酸、プルリオールＥ４００－ジカルボン酸、プルリオールＥ６００－ジカルボン酸、ピラゾール－３，４－ジカルボン酸、２，３－ピラジンジカルボン酸、５，６－ジメチル－２，３－ピラジンジカルボン酸、４，４’－ジアミノ（ジフェニルエーテル）ジイミドジカルボン酸、４，４’－ジアミノジフェニルメタンジイミドジカルボン酸、４，４’－ジアミノ（ジフェニルスルホン）ジイミドジカルボン酸、１，４－ナフタレンジカルボン酸、２，６－ナフタレンジカルボン酸、１，３－アダマンタンジカルボン酸、１，８－ナフタレンジカルボン酸、２，３－ナフタレンジカルボン酸、８－メトキシ－２，３－ナフタレンジカルボン酸、８－ニトロ－２，３－ナフタレンジカルボン酸、８－スルホ－２，３－ナフタレンジカルボン酸、アントラセン－２，３－ジカルボン酸、２’，３’－ジフェニル－ｐ－ターフェニル－４，４”－ジカルボン酸、（ジフェニルエーテル）－４，４’－ジカルボン酸、イミダゾール－４，５－ジカルボン酸、４（１Ｈ）－オキオチオクロメン－２，８－ジカルボン酸、５－ｔｅｒｔ－ブチル－１，３－ベンゼンジカルボン酸、７，８－キノリンジカルボン酸、４，５－イミダゾールジカルボン酸、４－シクロヘキセン－１，２－ジカルボン酸、ヘキサトリアコンタンジカルボン酸、テトラデドカンジカルボン酸、１，７－ヘプタンジカルボン酸、５－ヒドロキシ－１，３－ベンゼンジカルボン酸、２，５－ジヒドロキシ－１，４－ジカルボン酸、ピラジン－２，３－ジカルボン酸、フラン－２，５－ジカルボン酸、１－ノネン－６，９－ジカルボン酸、エイコセンジカルボン酸、４，４’－ジヒドロキシジフェニルメタン－３，３’－ジカルボン酸、１－アミノ－４－メチル－９，１０－ジオキソ－９，１０－ジヒドロアントラセン－２，３－ジカルボン酸、２，５－ピリジンジカルボン酸、シクロヘキセン－２，３－ジカルボン酸、２，９－ジクロロフルオルビン－４，１１－ジカルボン酸、７－クロロ－３－メチルキノリン－６，８－ジカルボン酸、２，４－ジクロロベンゾフェノン－２’，５’－ジカルボン酸、１，３－ベンゼンジカルボン酸、２，６－ピリジンジカルボン酸、１－メチルピロール－３，４－ジカルボン酸、１－ベンジル－１Ｈ－ピロール－３，４－ジカルボン酸、アントラキノン－１，５－ジカルボン酸、３，５－ピラゾールジカルボン酸、２－ニトロベンゼン－１，４－ジカルボン酸、ヘプタン－１，７－ジカルボン酸、シクロブタン－１，１－ジカルボン酸、１，１４－テトラデドカンジカルボン酸、５，６－デヒドロノルボルナン－２，３－ジカルボン酸、５－エチル－２，３－ピリジンジカルボン酸、およびカンファージカルボン酸が挙げられる。 Examples of the dicarboxylic acids include oxalic acid, succinic acid, tartaric acid, maleic acid, 1,4-butanedicarboxylic acid, 1,4-butenedicarboxylic acid, 4-oxopyran-2,6-dicarboxylic acid, 1,6- Hexanedicarboxylic acid, decanedicarboxylic acid, 1,8-heptadecanedicarboxylic acid, 1,9-heptadecanedicarboxylic acid, heptadecanedicarboxylic acid, acetylenedicarboxylic acid, 1,2-benzenedicarboxylic acid, 1,3-benzenedicarboxylic acid , 2,3-pyridinedicarboxylic acid, pyridine-2,3-dicarboxylic acid, 1,3-butadiene-1,4-dicarboxylic acid, 1,4-benzenedicarboxylic acid, p-benzenedicarboxylic acid, imidazole-2,4 -dicarboxylic acid, 2-methylquinoline-3,4-dicarboxylic acid, quinoline-2,4-dicarboxylic acid, quinoxaline-2,3-dicarboxylic acid, 6-chloroquinoxaline-2,3-dicarboxylic acid, 4,4' -diaminophenylmethane-3,3'-dicarboxylic acid, quinoline-3,4-dicarboxylic acid, 7-chloro-4-hydroxyquinoline-2,8-dicarboxylic acid, diimidodicarboxylic acid, pyridine-2,6-dicarboxylic acid , 2-methylimidazole-4,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, 2-isopropylimidazole-4,5-dicarboxylic acid, tetrahydropyran-4,4-dicarboxylic acid, perylene-3,9 -dicarboxylic acid, perylene dicarboxylic acid, Pluriol E200-dicarboxylic acid, 3,6-dioxaoctane dicarboxylic acid, 3,5-cyclohexadiene-1,2-dicarboxylic acid, octane dicarboxylic acid, pentane-3,3-dicarboxylic acid , 4,4'-diamino-1,1'-biphenyl-3,3'-dicarboxylic acid, 4,4'-diaminobiphenyl-3,3'-dicarboxylic acid, benzidine-3,3'-dicarboxylic acid, 1 , 4-bis(phenylamino)benzene-2,5-dicarboxylic acid, 1,1'-binaphthyldicarboxylic acid, 7-chloro-8-methylquinoline-2,3-dicarboxylic acid, 1-anilino-anthraquinone-2, 4'-dicarboxylic acid, polytetrahydrofuran 250-dicarboxylic acid, 1,4-bis(carboxymethyl)piperazine-2,3-dicarboxylic acid, 7-chloroquinoline-3,8-dicarboxylic acid, 1-(4-carboxylic) Phenyl-3-(4-chloro)phenylpyrazoline-4,5-dicarboxylic acid, 1,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic acid, phenylindanedicarboxylic acid, 1,3-dibenzyl-2-oxoimidazolidine-4,5-dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, naphthalene-1,8-dicarboxylic acid, 2-benzoylbenzene-1,3-dicarboxylic acid, 1, 3-dibenzyl-2-oxoimidazolidene-4,5-cis-dicarboxylic acid, 2,2'-biquinoline-4,4'-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, 3,6,9-trio Xaoundecane dicarboxylic acid, hydroxybenzophenone dicarboxylic acid, Pluriol E300-dicarboxylic acid, Pluriol E400-dicarboxylic acid, Pluriol E600-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, 2,3-pyrazinedicarboxylic acid, 5,6-dimethyl -2,3-pyrazine dicarboxylic acid, 4,4'-diamino(diphenyl ether) diimide dicarboxylic acid, 4,4'-diaminodiphenylmethane diimide dicarboxylic acid, 4,4'-diamino(diphenylsulfone) diimide dicarboxylic acid, 1,4 -Naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 1,3-adamantanedicarboxylic acid, 1,8-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 8-methoxy-2,3-naphthalene dicarboxylic acid, 8 -Nitro-2,3-naphthalene dicarboxylic acid, 8-sulfo-2,3-naphthalene dicarboxylic acid, anthracene-2,3-dicarboxylic acid, 2',3'-diphenyl-p-terphenyl-4,4"- Dicarboxylic acid, (diphenyl ether)-4,4'-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, 4(1H)-okiothiochromene-2,8-dicarboxylic acid, 5-tert-butyl-1,3 -Benzenedicarboxylic acid, 7,8-quinolinedicarboxylic acid, 4,5-imidazoledicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, hexatriacontanedicarboxylic acid, tetradedocanedicarboxylic acid, 1,7-heptanedicarboxylic acid acid, 5-hydroxy-1,3-benzenedicarboxylic acid, 2,5-dihydroxy-1,4-dicarboxylic acid, pyrazine-2,3-dicarboxylic acid, furan-2,5-dicarboxylic acid, 1-nonene-6 , 9-dicarboxylic acid, eicosene dicarboxylic acid, 4,4'-dihydroxydiphenylmethane-3,3'-dicarboxylic acid, 1-amino-4-methyl-9,10-dioxo-9,10-dihydroanthracene-2, 3-dicarboxylic acid, 2,5-pyridinedicarboxylic acid, cyclohexene-2,3-dicarboxylic acid, 2,9-dichlorofluorobin-4,11-dicarboxylic acid, 7-chloro-3-methylquinoline-6,8- Dicarboxylic acid, 2,4-dichlorobenzophenone-2',5'-dicarboxylic acid, 1,3-benzenedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 1-methylpyrrole-3,4-dicarboxylic acid, 1-benzyl -1H-pyrrole-3,4-dicarboxylic acid, anthraquinone-1,5-dicarboxylic acid, 3,5-pyrazoledicarboxylic acid, 2-nitrobenzene-1,4-dicarboxylic acid, heptane-1,7-dicarboxylic acid, cyclobutane -1,1-dicarboxylic acid, 1,14-tetradedokanedicarboxylic acid, 5,6-dehydronorbornane-2,3-dicarboxylic acid, 5-ethyl-2,3-pyridinedicarboxylic acid, and camphordicarboxylic acid. It will be done.
上記トリカルボン酸としては、例えば、２－ヒドロキシ－１，２，３－プロパントリカルボン酸、７－クロロ－２，３，８－キノリントリカルボン酸、１，２，３－、１，２，４－ベンゼントリカルボン酸、１，２，４－ブタントリカルボン酸、２－ホスフォノ－１，２，４－ブタントリカルボン酸、１，３，５－ベンゼントリカルボン酸、４，４’，４”－（１，３，５－ベンゼントリイル）トリス安息香酸、１－ヒドロキシ－１，２，３－プロパントリカルボン酸、４，５－ジヒドロ－４，５－ジオキソ－１Ｈ－ピロロ［２，３－Ｆ］キノリン－２，７，９－トリカルボン酸、５－アセチル－３－アミノ－６－メチルベンゼン－１，２，４－トリカルボン酸、３－アミノ－５－ベンゾイル－６－メチルベンゼン－１，２，４－トリカルボン酸、１，２，３－プロパントリカルボン酸、およびオーリントリカルボン酸が挙げられる。 Examples of the above tricarboxylic acids include 2-hydroxy-1,2,3-propanetricarboxylic acid, 7-chloro-2,3,8-quinolinetricarboxylic acid, 1,2,3-,1,2,4-benzene Tricarboxylic acid, 1,2,4-butanetricarboxylic acid, 2-phosphono-1,2,4-butanetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 4,4',4''-(1,3, 5-benzentriyl) trisbenzoic acid, 1-hydroxy-1,2,3-propanetricarboxylic acid, 4,5-dihydro-4,5-dioxo-1H-pyrrolo[2,3-F]quinoline-2, 7,9-tricarboxylic acid, 5-acetyl-3-amino-6-methylbenzene-1,2,4-tricarboxylic acid, 3-amino-5-benzoyl-6-methylbenzene-1,2,4-tricarboxylic acid , 1,2,3-propanetricarboxylic acid, and aurinetricarboxylic acid.
上記テトラカルボン酸としては、１，１－ジオキシドペリロ［１，１２－ＢＣＤ］チオフェン－３，４，９，１０－テトラカルボン酸、ペリレン－３，４，９，１０－テトラカルボン酸または（ペリレン－１，１２－スルホン）－３，４，９，１０－テトラカルボン酸などのペリレンテトラカルボン酸、１，２，３，４－ブタンテトラカルボン酸またはメソ－１，２，３，４－ブタンテトラカルボン酸などのブタンテトラカルボン酸、デカン－２，４，６，８－テトラカルボン酸、１，４，７，１０，１３，１６－ヘキサオキサシクロオクタデカン－２，３，１１，１３－テトラカルボン酸、１，２，４，５－ベンゼンテトラカルボン酸、１，２，１１，１２－ドデカンテトラカルボン酸、１，２，５，６－ヘキサンテトラカルボン酸、１，２，７，８－オクタンテトラカルボン酸、１，４，５，８－ナフタレンテトラカルボン酸、１，２，９，１０－デカンテトラカルボン酸、ベンゾフェノンテトラカルボン酸、３，３’，４，４’－ベンゾフェノンテトラカルボン酸、テトラヒドロフランテトラカルボン酸、およびシクロペンタン－１，２，３，４－テトラカルボン酸などのシクロペンタンテトラカルボン酸が挙げられる。 The above-mentioned tetracarboxylic acid includes 1,1-dioxidoperillo[1,12-BCD]thiophene-3,4,9,10-tetracarboxylic acid, perylene-3,4,9,10-tetracarboxylic acid, or (perylene- Perylenetetracarboxylic acids such as 1,12-sulfone)-3,4,9,10-tetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid or meso-1,2,3,4-butanetetracarboxylic acid Carboxylic acids such as butanetetracarboxylic acid, decane-2,4,6,8-tetracarboxylic acid, 1,4,7,10,13,16-hexaoxacyclooctadecane-2,3,11,13-tetracarboxylic acid acid, 1,2,4,5-benzenetetracarboxylic acid, 1,2,11,12-dodecanetetracarboxylic acid, 1,2,5,6-hexanetetracarboxylic acid, 1,2,7,8-octane Tetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,9,10-decanetetracarboxylic acid, benzophenonetetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, Examples include cyclopentanetetracarboxylic acids such as tetrahydrofurantetracarboxylic acid and cyclopentane-1,2,3,4-tetracarboxylic acid.
一の態様において、上記有機配位子は、環ヘテロ原子により配位結合を形成することができる複素環に由来する。かかる複素環としては以下の複素環が挙げられる。該複素環は、非置換であっても置換されていてもよい。 In one embodiment, the organic ligand is derived from a heterocycle capable of forming coordination bonds through ring heteroatoms. Such heterocycles include the following heterocycles. The heterocycle may be unsubstituted or substituted.
好ましい態様において、上記有機配位子は、１，４－ベンゼンジカルボン酸、１，２－ベンゼンジカルボン酸、マレイン酸、１，３，５－ベンゼントリカルボン酸、４，４’，４”－（１，３，５－ベンゼントリイル）トリス安息香酸、４，４’－ビピリジン、トリアゾール、イミダゾール、３，３’－ビピラゾール、ベンゾイミダゾール、および３，５－ピリジンジカルボン酸から選択される。 In a preferred embodiment, the organic ligand is 1,4-benzenedicarboxylic acid, 1,2-benzenedicarboxylic acid, maleic acid, 1,3,5-benzenedicarboxylic acid, 4,4',4"-(1 , 3,5-benzenetriyl)trisbenzoic acid, 4,4'-bipyridine, triazole, imidazole, 3,3'-bipyrazole, benzimidazole, and 3,5-pyridinedicarboxylic acid.
上記の有機配位子は、１種のみであっても、２種以上であってもよい。 The number of the above-mentioned organic ligands may be one, or two or more.
尚、本明細書において「由来する」とは、所定の化合物そのものに加え、かかる化合物の一部がプロトン化した形態、完全にプロトン化した形態を含むことを意味する。 In addition, in this specification, "derived from" means that in addition to the predetermined compound itself, such a compound includes a partially protonated form and a completely protonated form.
上記有機配位子を含む溶液の溶媒は、例えば、エタノール、ジメチルホルムアミド、トルエン、メタノール、クロロベンゼン、ジエチルホルムアミド、ジメチルスルホキシド、水、過酸化水素、メチルアミン、水酸化ナトリウム溶液、Ｎ－メチルピロリドンエーテル、アセトニトリル、塩化ベンジル、トリエチルアミン、もしくはエチレングリコール、またはこれらの混合物であり得る。 Examples of the solvent for the solution containing the organic ligand include ethanol, dimethylformamide, toluene, methanol, chlorobenzene, diethylformamide, dimethyl sulfoxide, water, hydrogen peroxide, methylamine, sodium hydroxide solution, and N-methylpyrrolidone ether. , acetonitrile, benzyl chloride, triethylamine, or ethylene glycol, or mixtures thereof.
上記金属イオンを含む溶液の溶媒と上記有機配位子を含む溶液の溶媒は、同じであっても、異なっていてもよいが、好ましくは同じである。 The solvent of the solution containing the metal ion and the solvent of the solution containing the organic ligand may be the same or different, but are preferably the same.
上記有機配位子を含む溶液は、好ましくは５～３０質量％、より好ましくは１０～２０質量％であり得る。 The solution containing the organic ligand may preferably have a concentration of 5 to 30% by weight, more preferably 10 to 20% by weight.
上記有機配位子を含む溶液は、他の成分として、触媒、塩基等を含んでいてもよい。 The solution containing the organic ligand may also contain a catalyst, a base, etc. as other components.
工程１ａまたは工程１ｂで処理された金属基板の表面を、少なくとも１種の金属イオンを含む溶液および少なくとも１種の有機配位子を含む溶液と接触させる方法は、金属基材上に金属有機構造体が形成される限り特に限定されない。 The method of contacting the surface of the metal substrate treated in step 1a or step 1b with a solution containing at least one type of metal ion and a solution containing at least one type of organic ligand includes forming a metal-organic structure on the metal substrate. There is no particular limitation as long as the body is formed.
例えば、上記の処理は、上記金属基材を、金属イオンの溶液および有機配位子の溶液に浸漬することにより行ってもよく、あるいは、スプレー等により、上記金属基材の表面に金属イオンの溶液および有機配位子の溶液を塗布することにより行ってもよい。 For example, the above treatment may be performed by immersing the metal base material in a solution of metal ions and a solution of organic ligands, or by spraying or the like, applying metal ions to the surface of the metal base material. This may be carried out by applying a solution and a solution of the organic ligand.
上記の処理は、金属基材を、金属イオンの溶液および有機配位子の溶液のそれぞれと別個に接触させることにより行ってもよく、同時に接触させてもよい。 The above treatment may be performed by bringing the metal substrate into contact with the metal ion solution and the organic ligand solution, respectively, or simultaneously.
一の態様において、金属基材を、金属イオンの溶液および有機配位子の溶液の混合溶液に接触させてもよい。 In one embodiment, the metal substrate may be contacted with a mixed solution of a metal ion solution and an organic ligand solution.
別の態様において、金属基材を、有機配位子の溶液に接触させ、次いで、金属イオンの溶液に接触させてもよい。 In another embodiment, a metal substrate may be contacted with a solution of organic ligands and then a solution of metal ions.
別の態様において、金属基材を、金属イオンの溶液に接触させ、次いで、有機配位子の溶液に接触させてもよい。 In another embodiment, a metal substrate may be contacted with a solution of metal ions and then a solution of organic ligands.
別の態様において、金属基材を、金属イオンの溶液と有機配位子の溶液と、交互に複数回、接触させてもよい。かかる場合、金属イオンの溶液および有機配位子の溶液は、それぞれ、同じ溶液を用いてもよく、別の溶液を用いてもよい。例えば、最初にある金属イオンの溶液（例えば金属基材の金属と同じ金属のイオンを含む溶液）を用い、その後の別の金属イオンの溶液を用いてもよい。 In another embodiment, the metal substrate may be alternately contacted with a solution of metal ions and a solution of organic ligand multiple times. In such a case, the metal ion solution and the organic ligand solution may be the same solution or different solutions. For example, a solution of a certain metal ion (for example, a solution containing ions of the same metal as the metal of the metal base material) may be used first, and then a solution of another metal ion may be used.
かかる処理において、処理温度は、好ましくは１０～１００℃、より好ましくは２０～４０℃である。 In such treatment, the treatment temperature is preferably 10 to 100°C, more preferably 20 to 40°C.
かかる処理において、処理時間は、好ましくは１５～１２０分、より好ましくは６０～１２０分である。 In such a treatment, the treatment time is preferably 15 to 120 minutes, more preferably 60 to 120 minutes.
以上のようにして、工程１ａまたは工程１ｂおよび工程２を行うことにより、金属基材の表面に金属有機構造体の層を形成することができる。 By performing Step 1a or Step 1b and Step 2 as described above, a layer of a metal organic structure can be formed on the surface of a metal base material.
得られる金属有機構造体の層の厚みは、特に限定されないが、例えば１μｍ～１０ｍｍ、好ましくは１００μｍ～５ｍｍ、より好ましくは５００μｍ～２ｍｍであり得る。 The thickness of the layer of the metal-organic structure obtained is not particularly limited, but may be, for example, 1 μm to 10 mm, preferably 100 μm to 5 mm, more preferably 500 μm to 2 mm.
上記金属有機構造体の形成は、Ｘ線回折、Ｘ線光電子分光（ＸＰＳ）、走査電子顕微鏡（ＳＥＭ）観察などにより確認することができる。 The formation of the metal-organic structure can be confirmed by X-ray diffraction, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and the like.
本開示の方法において、上記の工程１ａ、工程１ｂおよび工程２は、適宜、後処理を含んでいてもよい。 In the method of the present disclosure, Step 1a, Step 1b, and Step 2 described above may include post-treatment as appropriate.
例えば、工程２の接触処理の後に、加熱処理を行ってもよい。 For example, heat treatment may be performed after the contact treatment in step 2.
本開示の方法によれば、金属基材からの金属有機構造体の剥離が抑制された積層体を得ることができる。本開示はいかなる理論にも拘束されないが、剥離が抑制される理由は以下のように考えられる。工程１ａを行う場合、工程１ａにおいて金属基材の表面に、金属基材由来の金属イオンが形成され、工程２において該金属イオンを起点として金属有機構造体が形成されると考えられる。換言すれば、金属基材の表面の原子が、金属有機構造体の一部を構成し、金属基材と金属有機構造体が一体となった状態にあると言える。また、工程１ｂを行う場合、工程１ｂにおいて金属基材の表面が修飾され、次いで金属層が形成され、この金属層の金属イオンを起点として金属有機構造体が形成されると考えられる。即ち、金属有機構造体は金属層と一体となるように形成されており、金属基材はその修飾表面により有機金属構造体を保持した状態にあると考えられる。換言すれば、金属基材、金属層および有機金属構造体は、一体となった状態にあると言える。即ち、本開示の積層体において、金属基材と有機金属構造体は、直接結合して、または金属層を介して結合して一体となった状態にある。 According to the method of the present disclosure, it is possible to obtain a laminate in which peeling of the metal organic structure from the metal base material is suppressed. Although the present disclosure is not bound by any theory, the reason why peeling is suppressed is thought to be as follows. When performing step 1a, it is thought that metal ions derived from the metal base material are formed on the surface of the metal base material in step 1a, and a metal-organic structure is formed in step 2 using the metal ions as a starting point. In other words, it can be said that the atoms on the surface of the metal base constitute a part of the metal-organic structure, and the metal base and the metal-organic structure are in an integrated state. Further, when performing step 1b, it is considered that the surface of the metal base material is modified in step 1b, a metal layer is then formed, and a metal-organic structure is formed using the metal ions of this metal layer as a starting point. That is, the metal-organic structure is formed integrally with the metal layer, and the metal base material is considered to be in a state in which the metal-organic structure is held by its modified surface. In other words, it can be said that the metal base material, the metal layer, and the organometallic structure are in an integrated state. That is, in the laminate of the present disclosure, the metal base material and the organometallic structure are in an integrated state by being directly bonded or bonded via a metal layer.
本開示は、本開示の製造方法により得られる積層体も含む。 The present disclosure also includes a laminate obtained by the manufacturing method of the present disclosure.
一の態様において、本開示は、
金属基材と上記金属基材上に形成された金属有機構造体とを有してなる積層体であって、金属基材上に、金属基材と一体となるように金属有機構造体が形成されている積層体
を含む。In one aspect, the present disclosure provides:
A laminate comprising a metal base material and a metal organic structure formed on the metal base material, the metal organic structure being formed on the metal base material so as to be integrated with the metal base material. Including laminates that are
一の態様において、本開示は、
金属基材と該金属基材上に形成された金属有機構造体とを有してなる積層体であって、上記金属基材の表面の金属原子が、上記金属有機構造体の一部を構成している積層体
を含む。In one aspect, the present disclosure provides:
A laminate comprising a metal base material and a metal organic structure formed on the metal base material, wherein metal atoms on the surface of the metal base constitute a part of the metal organic structure. Including laminates that are
一の態様において、本開示は、
金属基材と該金属基材上に形成された金属有機構造体とを有してなる積層体であって、上記金属基材の表面が修飾されており、該修飾された表面上に金属層を有し、該金属層上に金属有機構造体が形成されている、積層体
を含む。かかる積層体においては、好ましくは、金属基材は、金属層と修飾部により化学的に結合しており、さらに金属層の金属原子が、上記金属有機構造体の一部を構成している。In one aspect, the present disclosure provides:
A laminate comprising a metal base material and a metal organic structure formed on the metal base material, the surface of the metal base material being modified, and a metal layer on the modified surface. and a metal-organic structure is formed on the metal layer. In such a laminate, preferably, the metal base material is chemically bonded to the metal layer through the modification portion, and further, the metal atoms of the metal layer constitute a part of the metal-organic structure.
本開示の積層体は、金属基材と金属有機構造体間の密着性が高い。従って、本開示の積層体は、耐久性が求められる用途、例えば調湿用途等においても好適に用いることができる。また、本開示の積層体は、金属有機構造体の層の剥離が生じにくいことから複雑な形状の基材であっても適用することができる。かかる観点からも、フィン形状等、表面積を大きくするために複雑な形状が求められる調湿または熱交換に適していると言える。 The laminate of the present disclosure has high adhesion between the metal base material and the metal organic structure. Therefore, the laminate of the present disclosure can also be suitably used in applications where durability is required, such as humidity control applications. Further, the laminate of the present disclosure can be applied even to a base material having a complicated shape, since the metal-organic structure layer does not easily peel off. From this point of view, it can be said that it is suitable for humidity control or heat exchange which requires a complex shape such as a fin shape to increase the surface area.
従って、本開示は、本開示の積層体から構成されるフィンを含む。 Accordingly, the present disclosure includes fins constructed from the laminates of the present disclosure.
また、本開示は、本開示の積層体から構成されるフィンを有してなる、除加湿器を含む。 Further, the present disclosure includes a dehumidifier having a fin made of the laminate of the present disclosure.
また、本開示は、本開示の積層体から構成されるフィンを有してなる、熱交換器を含む。 The present disclosure also includes a heat exchanger having fins made of the laminate of the present disclosure.
実施例１
金属基材として、Ａｌのテストピースを準備した。前処理として、上記金属基材を、アセトン中で３０分間超音波洗浄し、次いで、ＨＦＥ７２００に浸漬した後、乾燥させた。
次いで、各金属基材をＨＦ溶液に３０分間浸漬し、その後、Ａｌ（ＮＯ３）３・９Ｈ２Ｏ（５．４３ｇ，２５ｍｍｏｌ）の水溶液（５０ｍＬ）に金属基材を浸漬させた。ＮａＯＨ（６．０ｇ，３ｅｑ，１５０ｍｍｏｌ）およびテレフタル酸（８．３ｇ，５０ｍｍｏｌ）を溶解した水溶液（８０ｍＬ）を加え、１００℃で１２時間加熱した。
後処理として、金属基材の表面をメタノールで洗浄し、７０℃で加熱乾燥し、金属基材上に金属有機構造体の層を形成した。Example 1
An Al test piece was prepared as a metal base material. As a pretreatment, the metal base material was ultrasonically cleaned in acetone for 30 minutes, then immersed in HFE7200, and then dried.
Next, each metal substrate was immersed in an HF solution for 30 minutes, and then in an aqueous solution (50 mL) of Al(NO 3 ) 3.9H 2 O (5.43 g, 25 mmol). An aqueous solution (80 mL) in which NaOH (6.0 g, 3 eq, 150 mmol) and terephthalic acid (8.3 g, 50 mmol) were dissolved was added, and the mixture was heated at 100° C. for 12 hours.
As a post-treatment, the surface of the metal base material was washed with methanol and dried by heating at 70°C to form a layer of the metal organic structure on the metal base material.
実施例２
金属基材としてＦｅのテストピースを用いた以外は、実施例１と同様にして、金属基材の表面に金属有機構造体の層を形成した。Example 2
A layer of a metal-organic structure was formed on the surface of a metal base material in the same manner as in Example 1 except that an Fe test piece was used as the metal base material.
実施例３
金属基材をＨＦに浸漬する代わりに、金属基材の表面にＵＶ－Ｏ３（テクノビジョン社製ＵＶ－オゾン照射装置）を１０分間照射した以外は、実施例１と同様にして、金属基材の表面に金属有機構造体の層を形成した。Example 3
A metal substrate was prepared in the same manner as in Example 1, except that instead of immersing the metal substrate in HF, the surface of the metal substrate was irradiated with UV-O 3 (UV-ozone irradiation device manufactured by Technovision) for 10 minutes. A layer of metal-organic structure was formed on the surface of the material.
実施例４
金属基材としてＦｅのテストピースを用いた以外は、実施例３と同様にして、金属基材の表面に金属有機構造体の層を形成した。Example 4
A layer of a metal-organic structure was formed on the surface of a metal base material in the same manner as in Example 3, except that an Fe test piece was used as the metal base material.
実施例５
枝付試験管に、ポリ（エチレングリコール）メタクリレート（シグマアルドリッチ製、以下、「ＰＥＧＭＡ」と称する）（１９．４ｇ）、メタクリロイルオキシエチルフォスフェート（東邦化学工業製、以下、「ＰＰＭＥ」と称する）（０．６ｇ）、およびイソプロピルエーテル（以下「ＩＰＡ」と称する）（８０ｇ）を仕込み、１０分間窒素バージし、７０℃に加熱した。次いで、アゾビスイソブチロニトリル（以下、「ＡＩＢＮ」と称する）（０．１１６１ｇ）を加え、６時間反応させて、ＰＥＧ－ＰＰＭＥ重合体（重合比９７／３）の溶液（樹脂固形分濃度０．５重量％）を得た。Example 5
In a test tube with a branch, poly(ethylene glycol) methacrylate (manufactured by Sigma-Aldrich, hereinafter referred to as "PEGMA") (19.4 g), methacryloyloxyethyl phosphate (manufactured by Toho Chemical Industries, hereinafter referred to as "PPME") (0.6 g) and isopropyl ether (hereinafter referred to as "IPA") (80 g) were charged, and the mixture was purged with nitrogen for 10 minutes and heated to 70°C. Next, azobisisobutyronitrile (hereinafter referred to as "AIBN") (0.1161 g) was added and reacted for 6 hours to reduce the solution (resin solid content concentration) of PEG-PPME polymer (polymerization ratio 97/3). 0.5% by weight).
金属基材として、Ａｌのテストピースを準備した。前処理として、上記金属基材を、アセトン中で３０分間超音波洗浄し、次いで、ＨＦＥ７２００に浸漬した後、乾燥させた。次いで、金属基材を、上記で得られたＰＥＧＭＡ／ＰＰＭＡ重合体の溶液に浸漬した後、大気中（２０℃、湿度３０％）で一昼夜放置して、ＰＥＧコート基材を得た。 An Al test piece was prepared as a metal base material. As a pretreatment, the metal base material was ultrasonically cleaned in acetone for 30 minutes, then immersed in HFE7200, and then dried. Next, the metal base material was immersed in the solution of the PEGMA/PPMA polymer obtained above, and then left in the atmosphere (20° C., humidity 30%) overnight to obtain a PEG coated base material.
次に、アルミニウムブトキシド（７５ｍｇ）をエタノール（１０ｍＬ）に加え、１時間超音波処理して、アルミニウムブトキシド／エタノール溶液を得た。次いで、上記で得られたＰＥＧコート基材をエタノールで３回洗浄し水を除去した後、上記アルミニウムブトキシド／エタノール溶液に浸漬し、超音波で１時間処理した。 Next, aluminum butoxide (75 mg) was added to ethanol (10 mL) and sonicated for 1 hour to obtain an aluminum butoxide/ethanol solution. Next, the PEG-coated substrate obtained above was washed three times with ethanol to remove water, and then immersed in the aluminum butoxide/ethanol solution and treated with ultrasound for 1 hour.
次に、Ａｌ（ＮＯ３）３・９Ｈ２Ｏ（５．４３ｇ，２５ｍｍｏｌ）の水溶液（５０ｍＬ）に、金属基材を浸漬させ、ＮａＯＨ（６．０ｇ，３ｅｑ，１５０ｍｍｏｌ）およびテレフタル酸（８．３ｇ，５０ｍｍｏｌ）を溶解した水溶液８０ｍＬを加え、１００℃で１２時間加熱した。その後、メタノールにて表面を洗浄し、７０℃で加熱乾燥して、金属基材上に金属有機構造体の層を形成した。Next, the metal substrate was immersed in an aqueous solution (50 mL) of Al(NO 3 ) 3.9H 2 O (5.43 g, 25 mmol), and NaOH (6.0 g, 3 eq, 150 mmol) and terephthalic acid (8. 3 g, 50 mmol) was added thereto, and the mixture was heated at 100° C. for 12 hours. Thereafter, the surface was washed with methanol and dried by heating at 70° C. to form a layer of the metal-organic structure on the metal base material.
比較例１
金属基材をＨＦに浸漬する処理を行わないこと以外は、実施例１と同様にして、金属基材の表面に金属有機構造体の層を形成した。Comparative example 1
A layer of a metal organic structure was formed on the surface of a metal base material in the same manner as in Example 1 except that the metal base material was not immersed in HF.
比較例２
Ａｌ（ＮＯ３）３およびテレフタル酸から別途錯体を形成し、得られた錯体とバインダーとしてのウレタン樹脂を混合し、そこに金属基材を浸漬することにより、金属基材の表面に金属有機構造体の層を形成した。Comparative example 2
A complex is separately formed from Al(NO 3 ) 3 and terephthalic acid, the resulting complex is mixed with a urethane resin as a binder, and the metal substrate is immersed therein to form a metal-organic structure on the surface of the metal substrate. formed layers of the body.
耐久性試験
実施例１～５および比較例１～２で得られた積層体を、それぞれ、７０℃の温水に１５００時間浸漬させた。その後、表面のＭＯＦの剥がれを目視で観察した。また、浸漬前後での基材の重量変化率を求めた。結果を下記表に示す。Durability Test The laminates obtained in Examples 1 to 5 and Comparative Examples 1 to 2 were each immersed in hot water at 70°C for 1500 hours. Thereafter, peeling of the MOF on the surface was visually observed. In addition, the weight change rate of the base material before and after dipping was determined. The results are shown in the table below.
上記の結果から、金属有機構造体の形成前に、金属表面を活性化した本開示の積層体は、剥がれが少なく、密着性が高いことが示された。 The above results showed that the laminate of the present disclosure in which the metal surface was activated before the formation of the metal-organic structure had less peeling and high adhesion.
本開示の金属基材とその上に形成された金属有機構造体とを有してなる積層体は、吸着材、触媒などに好適に用いることができる。 A laminate including the metal base material of the present disclosure and a metal organic structure formed thereon can be suitably used as an adsorbent, a catalyst, and the like.
Claims (8)
（工程１ａ）金属基材の表面を活性化する工程、および
（工程２）上記金属基材の表面を、少なくとも１種の金属イオンを含む溶液および少なくとも１種の有機配位子を含む溶液と接触させ、金属基材上に金属有機構造体を形成する工程
を含み、
前記工程１ａの活性化により前記金属基材の表面に形成された金属イオンと、前記金属イオンを含む溶液中の金属イオンが同じである、
製造方法。 A method for producing a laminate comprising a metal base material and a metal organic structure formed thereon, the method comprising:
(Step 1a) Activating the surface of the metal substrate; and (Step 2) treating the surface of the metal substrate with a solution containing at least one metal ion and at least one organic ligand. contacting to form a metal-organic framework on the metal substrate;
The metal ions formed on the surface of the metal base material by the activation in step 1a and the metal ions in the solution containing the metal ions are the same.
Production method.
前記積層体は、金属基材と該金属基材上に形成された金属有機構造体とを有してなる積層体であって、前記金属基材を構成する金属は、Ｓｉ、Ａｌ、Ｃｕ、Ｆｅ、Ｎｉ、もしくはＺｎ、またはＦｅ／Ｎｉ／Ｃｒ合金であり、
前記金属有機構造体は、金属イオンと、有機配位子とを含み、
前記金属イオンが、Ｓｉ、Ａｌ、もしくはＦｅ、またはＦｅ／Ｎｉ／Ｃｒ合金に由来する金属イオンであって、前記有機配位子が、１，４－ベンゼンジカルボン酸、１，２－ベンゼンジカルボン酸、マレイン酸、１，３，５－ベンゼントリカルボン酸、４，４’，４”－（１，３，５－ベンゼントリイル）トリス安息香酸、４，４’－ビピリジン、トリアゾール、イミダゾール、３，３’－ビピラゾール、ベンゾイミダゾール、および３，５－ピリジンジカルボン酸からなる群より選択される少なくとも１種の化合物に由来するか、
前記金属イオンが、Ｚｎに由来する金属イオンであって、前記有機配位子が、１，４－ベンゼンジカルボン酸、１，２－ベンゼンジカルボン酸、マレイン酸、４，４’，４”－（１，３，５－ベンゼントリイル）トリス安息香酸、４，４’－ビピリジン、トリアゾール、イミダゾール、３，３’－ビピラゾール、ベンゾイミダゾール、および３，５－ピリジンジカルボン酸からなる群より選択される少なくとも１種の化合物に由来するか、
前記金属イオンが、Ｎｉに由来する金属イオンであって、前記有機配位子が、１，４－ベンゼンジカルボン酸、１，２－ベンゼンジカルボン酸、マレイン酸、４，４’，４”－（１，３，５－ベンゼントリイル）トリス安息香酸、４，４’－ビピリジン、トリアゾール、イミダゾール、３，３’－ビピラゾール、ベンゾイミダゾール、および３，５－ピリジンジカルボン酸からなる群より選択される少なくとも１種の化合物に由来するか、
前記金属イオンが、Ｃｕに由来する金属イオンであって、前記有機配位子が、１，２－ベンゼンジカルボン酸、マレイン酸、４，４’，４”－（１，３，５－ベンゼントリイル）トリス安息香酸、４，４’－ビピリジン、トリアゾール、イミダゾール、３，３’－ビピラゾール、ベンゾイミダゾール、および３，５－ピリジンジカルボン酸からなる群より選択される少なくとも１種の化合物に由来し、
上記金属基材の表面の金属原子が、上記金属有機構造体の一部を構成している、フィン。 Composed of laminates ,
The laminate is a laminate including a metal base material and a metal organic structure formed on the metal base material, and the metal constituting the metal base material is Si, Al, Cu, Fe, Ni, or Zn, or a Fe/Ni/Cr alloy;
The metal-organic structure includes a metal ion and an organic ligand,
The metal ion is a metal ion derived from Si, Al, or Fe, or a Fe/Ni/Cr alloy, and the organic ligand is 1,4-benzenedicarboxylic acid, 1,2-benzenedicarboxylic acid. , maleic acid, 1,3,5-benzenetricarboxylic acid, 4,4',4''-(1,3,5-benzenetriyl)trisbenzoic acid, 4,4'-bipyridine, triazole, imidazole, 3, derived from at least one compound selected from the group consisting of 3'-bipyrazole, benzimidazole, and 3,5-pyridinedicarboxylic acid,
The metal ion is a metal ion derived from Zn, and the organic ligand is 1,4-benzenedicarboxylic acid, 1,2-benzenedicarboxylic acid, maleic acid, 4,4',4''-( 1,3,5-benzentriyl)trisbenzoic acid, 4,4'-bipyridine, triazole, imidazole, 3,3'-bipyrazole, benzimidazole, and 3,5-pyridinedicarboxylic acid derived from at least one compound,
The metal ion is a metal ion derived from Ni, and the organic ligand is 1,4-benzenedicarboxylic acid, 1,2-benzenedicarboxylic acid, maleic acid, 4,4',4''-( 1,3,5-benzentriyl)trisbenzoic acid, 4,4'-bipyridine, triazole, imidazole, 3,3'-bipyrazole, benzimidazole, and 3,5-pyridinedicarboxylic acid derived from at least one compound,
The metal ion is a metal ion derived from Cu, and the organic ligand is 1,2-benzenedicarboxylic acid, maleic acid, 4,4',4"-(1,3,5-benzenedicarboxylic acid, derived from at least one compound selected from the group consisting of trisbenzoic acid, 4,4'-bipyridine, triazole, imidazole, 3,3'-bipyrazole, benzimidazole, and 3,5-pyridinedicarboxylic acid ,
A fin , wherein metal atoms on the surface of the metal base constitute a part of the metal-organic structure .
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