CN115975492A - Metal material surface treating agent and preparation method and application thereof - Google Patents
Metal material surface treating agent and preparation method and application thereof Download PDFInfo
- Publication number
- CN115975492A CN115975492A CN202310058652.XA CN202310058652A CN115975492A CN 115975492 A CN115975492 A CN 115975492A CN 202310058652 A CN202310058652 A CN 202310058652A CN 115975492 A CN115975492 A CN 115975492A
- Authority
- CN
- China
- Prior art keywords
- vanadium
- group
- metal material
- water
- silane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000007769 metal material Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 125000000524 functional group Chemical group 0.000 claims abstract description 33
- 239000012756 surface treatment agent Substances 0.000 claims abstract description 29
- -1 polysiloxane Polymers 0.000 claims abstract description 27
- 125000000129 anionic group Chemical group 0.000 claims abstract description 24
- 229910000077 silane Inorganic materials 0.000 claims abstract description 22
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 150000003682 vanadium compounds Chemical class 0.000 claims abstract description 18
- 239000000945 filler Substances 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 229920002635 polyurethane Polymers 0.000 claims abstract description 11
- 239000004814 polyurethane Substances 0.000 claims abstract description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 10
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 9
- 239000011737 fluorine Substances 0.000 claims abstract description 9
- 239000010703 silicon Substances 0.000 claims abstract description 9
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 12
- 229910052720 vanadium Inorganic materials 0.000 claims description 12
- 239000010935 stainless steel Substances 0.000 claims description 11
- 229910001220 stainless steel Inorganic materials 0.000 claims description 11
- 229910000838 Al alloy Inorganic materials 0.000 claims description 9
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 8
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 claims description 7
- 125000002091 cationic group Chemical group 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 5
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 claims description 5
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 claims description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 4
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 claims description 3
- UBEDKMYHTMGYIE-UHFFFAOYSA-N 1,2,3,4-tetramethyltetrasiletane Chemical compound C[SiH]1[SiH](C)[SiH](C)[SiH]1C UBEDKMYHTMGYIE-UHFFFAOYSA-N 0.000 claims description 3
- PAJMKGZZBBTTOY-UHFFFAOYSA-N 2-[[2-hydroxy-1-(3-hydroxyoctyl)-2,3,3a,4,9,9a-hexahydro-1h-cyclopenta[g]naphthalen-5-yl]oxy]acetic acid Chemical compound C1=CC=C(OCC(O)=O)C2=C1CC1C(CCC(O)CCCCC)C(O)CC1C2 PAJMKGZZBBTTOY-UHFFFAOYSA-N 0.000 claims description 3
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical group OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 239000003429 antifungal agent Substances 0.000 claims description 3
- 229940121375 antifungal agent Drugs 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 229920006317 cationic polymer Polymers 0.000 claims description 3
- 239000003086 colorant Substances 0.000 claims description 3
- BJZIJOLEWHWTJO-UHFFFAOYSA-H dipotassium;hexafluorozirconium(2-) Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[K+].[K+].[Zr+4] BJZIJOLEWHWTJO-UHFFFAOYSA-H 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 3
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 3
- 239000004014 plasticizer Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229910021332 silicide Inorganic materials 0.000 claims description 3
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 3
- 229940041260 vanadyl sulfate Drugs 0.000 claims description 3
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims description 3
- 239000003021 water soluble solvent Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 2
- 239000003242 anti bacterial agent Substances 0.000 claims description 2
- 230000000844 anti-bacterial effect Effects 0.000 claims description 2
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 2
- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical compound [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 claims 1
- 150000001722 carbon compounds Chemical class 0.000 claims 1
- 150000004697 chelate complex Chemical class 0.000 claims 1
- 229910017053 inorganic salt Inorganic materials 0.000 claims 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims 1
- JBIQAPKSNFTACH-UHFFFAOYSA-K vanadium oxytrichloride Chemical compound Cl[V](Cl)(Cl)=O JBIQAPKSNFTACH-UHFFFAOYSA-K 0.000 claims 1
- 238000000576 coating method Methods 0.000 description 25
- 239000000463 material Substances 0.000 description 24
- 239000011248 coating agent Substances 0.000 description 23
- 238000012360 testing method Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 238000013329 compounding Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 150000002222 fluorine compounds Chemical class 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- MFWFDRBPQDXFRC-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;vanadium Chemical compound [V].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MFWFDRBPQDXFRC-LNTINUHCSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- ZHXZNKNQUHUIGN-UHFFFAOYSA-N chloro hypochlorite;vanadium Chemical compound [V].ClOCl ZHXZNKNQUHUIGN-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000013527 degreasing agent Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 238000011463 hyperthermic intraperitoneal chemotherapy Methods 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- UPGSWASWQBLSKZ-UHFFFAOYSA-N 2-hexoxyethanol Chemical compound CCCCCCOCCO UPGSWASWQBLSKZ-UHFFFAOYSA-N 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- CXYAFFSHJZNAKZ-UHFFFAOYSA-N C[Si]1(O[Si](O[Si](O[Si](O1)(C)C)(C)C)(C)C)C.C[Si]1(O[Si](O[Si](O[Si](O1)(C)C)(C)C)(C)C)C Chemical compound C[Si]1(O[Si](O[Si](O[Si](O1)(C)C)(C)C)(C)C)C.C[Si]1(O[Si](O[Si](O[Si](O1)(C)C)(C)C)(C)C)C CXYAFFSHJZNAKZ-UHFFFAOYSA-N 0.000 description 1
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 description 1
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005237 degreasing agent Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- RXCBCUJUGULOGC-UHFFFAOYSA-H dipotassium;tetrafluorotitanium;difluoride Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[K+].[K+].[Ti+4] RXCBCUJUGULOGC-UHFFFAOYSA-H 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229910001039 duplex stainless steel Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910000734 martensite Inorganic materials 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
The invention discloses a metal material surface treating agent and a preparation method and application thereof, wherein the metal material surface treating agent comprises the following components in parts by weight: 8.0-67.0 percent of silane (K) modified filler (A) containing anionic functional groups, 5.0-48.0 percent of polysiloxane polymer (C), 0.3-5.0 percent of fluorine-containing compound (D), 0.4-9.0 percent of vanadium compound (E) and 19.0-85.0 percent of silicon modified polyurethane (F) with polysiloxane structure accounting for more than 30 percent of the total molecular weight. The metal material surface treatment agent is coated on the surface of the metal material, so that the metal material is endowed with excellent high heat resistance and high thermal conductivity.
Description
Technical Field
The invention relates to a coating, in particular to a metal material surface treating agent, a preparation method and application thereof.
Background
With the rapid development of modern electronic technology, the integration degree and the assembly density of electronic components are continuously improved, and the working power consumption and the heat productivity of the electronic components are also increased sharply while strong use functions are provided. High temperatures can have a detrimental effect on the stability, reliability and lifetime of electronic components. Therefore, the heat generated by the heating electronic components can be discharged in time, which has become the technical bottleneck problem of microelectronic products. In recent years, coatings having excellent thermal conductivity or heat dissipation have been developed (e.g., CN 110294987A and the like). However, the above-mentioned coating material cannot solve the problem of heat resistance after long-term use at high temperatures in the practical use of electronic components.
Disclosure of Invention
Aiming at the defects of the heat conducting or radiating coating of the metal surface in the prior art, the invention aims to provide a metal material surface treating agent with better adherence, heat resistance and heat conductivity. In order to realize the purpose of the invention, the invention adopts the following technical scheme:
a metal material surface treating agent comprises the following components in percentage by weight:
in some preferred embodiments of the present invention, in the silane (K) modified filler (a) containing an anionic functional group, the filler (a) is selected from the group consisting of graphene, graphite fibers, metal borides, metal carbides, nitrides and metal silicides in combination of one or more thereof.
In some preferred embodiments of the present invention, in the anionic functional group-containing silane (K) -modified filler (a), the anionic functional group-containing silane (K) has the structural formula (I): tx + My - (SiR 1 R 2 R 3 ) n ,
Wherein x is 1 to 2, y is 1 to 3, n is 1 to 50,
R 1 、R 2 、R 3 independently from each other, an alkyl group, an alicyclic group or an aromatic group having 1 to 20 carbon atoms;
t is hydrogen or a cationic functional group, wherein the cationic functional group is a group IA element ion, a group IIA element ion, a rare earth element ion, a quaternary ammonium salt or a cationic polymer; m is a sulfonic acid group (-SO) 3 - ) Sulfuric acid anion group (-OSO) 3 - ) Carboxyl (-COO) - ) Organic phosphorusAcid group (-PO) (-) 3 2- ) Or a phosphate group (-OPO) 3 2- )。
In some preferred embodiments of the present invention, the anionic functional group-containing silane (K) is present in the anionic functional group-containing silane (K) modified filler (A) in an amount of 0.2 to 20.0% by weight.
In some preferred embodiments of the present invention, the method for preparing the silane (K) containing an anionic functional group comprises the steps of:
reacting 1,3,5,7-tetravinyl tetramethylcyclotetrasilane (D4H) and alpha-methylstyrene (AMS) with a HIPEC 13100 platinum catalyst prepared by Johnson Matthey under nitrogen protection at 100-130 ℃ to obtain an intermediate, and reacting the intermediate with chlorosulfonic acid to obtain the silane containing an anionic functional group, wherein the molar ratio of the 1,3,5,7-tetravinyl tetramethylcyclotetrasilane to the alpha-methylstyrene is 1:3 to 5, more preferably 1:4, and wherein the molar ratio of the intermediate to chlorosulfonic acid is from 1 to 7, more preferably 1.
In some preferred embodiments of the present invention, the molecular structure of the polysiloxane polymer (C) comprises SiR 4 R 5 R 6 Structure (II) wherein R 4 、R 5 、R 6 Each independently selected from alkyl groups having 1 to 4 carbon atoms or hydroxyl groups, provided that R 4 、R 5 、R 6 Not simultaneously being hydroxyl.
In some preferred embodiments of the present invention, the fluorine-containing compound (D) is selected from a combination of one or more of titanium-containing fluoride, zirconium-containing fluoride, silicon-containing fluoride, hydrofluoric acid, ammonium fluoride and ammonium bifluoride.
In some preferred embodiments of the present invention, the titanium-containing fluoride is selected from one or more of fluotitanic acid, ammonium fluotitanate, potassium fluotitanate, and sodium fluotitanate.
In some preferred embodiments of the present invention, the zirconium-containing fluoride is selected from one or more of fluorozirconic acid, ammonium fluorozirconate, potassium fluorozirconate, and sodium fluorozirconate.
In some preferred embodiments of the present invention, the silicon-containing fluoride is selected from one or more of fluorosilicic acid, ammonium fluorosilicate, potassium fluorosilicate, and sodium fluorosilicate.
In some preferred embodiments of the present invention, the vanadium compound (E) is selected from the group consisting of vanadium alkoxides, vanadium-containing chelate complexes, inorganic salts of vanadium, organic salts of vanadium, and combinations of one or more of organic vanadium compounds and vanadium oxides.
In some preferred embodiments of the present invention, the vanadium compound (E) is selected from vanadium pentoxide (V) 2 O 5 ) Metavanadate (HVO) 3 ) Ammonium metavanadate, sodium metavanadate, potassium metavanadate, vanadium oxychloride (VOCl) 3 ) Vanadium (V) oxide 2 O 3 ) Vanadium dioxide (VO) 2 ) Vanadyl sulfate (VOSO) 4 ) Vanadyl acetylacetonate (VO (OC (= CH)) 2 )CH 2 COCH 3 ) 2 ) Vanadium acetylacetonate (V (OC (= CH)) 2 )CH 2 COCH 3 ) 3 ) Vanadium trichloride (VCl) 3 ) And phosphomolybdovanadophosphoric acid.
Preferably, the silicon-modified polyurethane (F) is a silicon-modified polyurethane (F) having a polysiloxane structure accounting for 30% or more of the total molecular weight, for example, 30% to 50%,30% to 40%, or 30% to 35% of the total molecular weight.
In some preferred embodiments of the present invention, the above metal material surface treatment agent further comprises one or more of the following components in combination:
water, an organic solvent, a pigment, a water-based lubricant, a resin hardening component, a plasticizer, a water-soluble solvent, a defoaming agent, an antibacterial and antifungal agent, and a coloring agent.
The invention also provides a preparation method of the metal material surface treating agent, which comprises the following steps: adding silane (K) modified filler (A) containing anionic functional groups, polysiloxane polymer (C), fluorine-containing compound (D), vanadium compound (E) and silicon modified polyurethane (F) into water or a mixture of water and organic solvent, and uniformly mixing, wherein the organic solvent is mutually soluble with the water, and the mass content of the water in the mixture of the water and the organic solvent is not less than 25%.
Another aspect of the invention providesThe surface treating agent is coated on the surface of the metal material, dried and formed into a film, wherein the film forming temperature (PMT) is controlled to be 60-200 ℃, and the amount of a dry film is 0.1-50 g/m 2 The metal material is copper, copper alloy, aluminum alloy and stainless steel.
In another aspect of the present invention, there is provided a metal material having a surface coated with a film formed by the above-mentioned metal material surface treatment agent, wherein the metal material is copper, a copper alloy, aluminum, an aluminum alloy and stainless steel.
Compared with the prior art, the metal material surface treating agent provided by the invention comprises the following components: good adhesion, heat resistance and thermal conductivity.
Detailed Description
The metal material surface treating agent comprises the following components in percentage by weight:
in the description of the present invention, the silane-modified filler (a) containing the anionic functional group (K) functions to provide the bonding force of the film formed of the surface treatment agent to the substrate and high heat release property. In the silane-modified filler (a) containing an anionic functional group (K), the silane (K) containing an anionic functional group has the formula: tx + My - (SiR 1 R 2 R 3 ) n Wherein R is 1 、R 2 、R 3 Each independently selected from an alkyl group having 1 to 20 carbon atoms, an alicyclic structure, and an aromatic structure. M is sulfonic acid group (-SO) 3 - ) Sulfuric acid anion group (-OSO) 3 - ) Carboxyl (-COO) - ) Organic phosphoric acid group (-PO) 3 2- ) Phosphate group (-OPO) 3 2- ). T is hydrogen or a cationic functional group. The cationic functional group is preferably an ion of a group IA element, an ion of a group IIA element, a rare earth element, a quaternary ammonium salt, a cationic polymer, or the like.
In the description of the present invention, the filler (a) includes, but is not limited to, graphene, graphite fiber, metal boride, metal carbide, nitride, metal silicide.
In the description of the present invention, the polysiloxane polymer (C) functions to provide a bonding force of a film formed of the surface treatment agent to a substrate and high heat resistance. The polysiloxane polymer (C) is produced by reacting a compound (H) having a reactive functional group (a) with a silane compound (S) having a functional group (b) capable of reacting with the reactive functional group (a). The resulting polysiloxane polymer (C) contains SiR in its molecular structure 4 R 5 R 6 The structure of (1). SiR 4 R 5 R 6 In the structure of (1), R 4 、R 5 、R 6 Each independently selected from an alkyl group having 1 to 4 carbon atoms or a hydroxyl group), provided that R is 4 、R 5 、R 6 Not both may be hydroxyl groups.
In the description of the present invention, the fluorine-containing compound (D) functions to provide the strength of the film formed by the surface treatment agent and the bonding force thereof to the metal substrate. The fluorine-containing compound (D) includes, but is not limited to, titanium-containing fluorides, zirconium-containing fluorides, silicon-containing fluorides, hydrofluoric acid, ammonium fluoride, ammonium bifluoride, and the like. The term "titanium-containing fluoride" refers to a fluorine compound containing a titanium atom, is not particularly limited, and is preferably water-soluble, for example, fluorotitanic acid, ammonium fluorotitanate, potassium fluorotitanate, sodium fluorotitanate, and the like. The term "zirconium-containing fluoride" refers to a fluorine compound containing a zirconium atom, and is not particularly limited, but is preferably water-soluble, for example, fluorozirconic acid, ammonium fluorozirconate, potassium fluorozirconate, sodium fluorozirconate, and the like. The term "silicon-containing fluoride" refers to a fluorine compound containing silicon atoms, and is not particularly limited, and is preferably water-soluble, for example, fluorosilicic acid, ammonium fluorosilicate, potassium fluorosilicate, sodium fluorosilicate and the like.
In the description of the present invention, the vanadium compound (E) functions to provide the adhesion of the film formed by the surface treatment agent to the substrate and the heat resistance. The vanadium compound (E) is a compound containing a vanadium atom, is not particularly limited, and is preferably water-soluble. Vanadium compounds (F) useful in the present invention, for example, vanadium alkoxides, chelate complexes containing vanadium, inorganic salts of vanadium, organic vanadium compounds andvanadium oxide, and the like. For example, vanadium pentoxide (V) 2 O 5 ) Metavanadate (HVO) 3 ) Ammonium metavanadate, sodium metavanadate, potassium metavanadate, vanadium oxychloride (VOCl) 3 ) Vanadium (V) oxide 2 O 3 ) Vanadium dioxide (VO) 2 ) Vanadyl sulfate (VOSO) 4 ) Vanadyl acetylacetonate (VO (OC (= CH)) 2 )CH 2 COCH 3 ) 2 ) Vanadium acetylacetonate (V (OC (= CH)) 2 )CH 2 COCH 3 ) 3 ) Vanadium trichloride (VCl) 3 ) Phosphomolybdovanadophosphoric acid, and the like. In the case of using a pentavalent vanadium compound, the compound can be used by reducing it to a tetravalent to divalent state by using an organic substance having a hydroxyl group, a carbonyl group, a carboxyl group, a1 to 3-stage amino group, an amide group, a phosphate group or a phosphonic acid group functional group. In the description of the present invention, the vanadium compound (E) may be a combination of one or more of the above specific vanadium compounds.
In the description of the present invention, the silicon-modified polyurethane (F) functions to provide toughness of a film formed by the surface treatment agent and its bonding force to the substrate. The silicon-modified polyurethane (F) may be cationic, nonionic or anionic. Preferably, the solubility of the water is 0.1g/1L or more in water having a temperature of 20 ℃. One or two or more of the urethane resins (F) may be used.
The compounding amount of each component in the metal material surface treating agent is as follows:
the Amount (TA) of the anionic functional group-containing silane (K) modified filler (A) and the Total Mass (TM) ((TM) is the total solid content of the surface treatment agent and is the same) are in a ratio of (TA)/(TM) of 8.0% to 67.0%, the ratio of the mass (TC) of the polysiloxane polymer (C) and the Total Mass (TM) (TC)/(TM) of 5.0% to 48.0%, the compounding amount (amount) of the fluorine-containing compound (D) is not particularly limited, but the ratio of the mass (TD) to the Total Mass (TM) (TC)/(TM) thereof is more preferably in the range of 0.3% to 5.0%, the compounding amount (amount) of the vanadium compound (E) is not particularly limited, but the ratio of the mass (TE) to the Total Mass (TM) (TE)/(TM) thereof is more preferably in the range of 0.4% to 9.0%, the compounding amount of the silicon-modified polyurethane (F) is not particularly limited, but the ratio of the mass (TF) to the Total Mass (TM) (TF) thereof and the Total Mass (TM) (TE)/(TM) thereof is preferably in the range of 0.19% to 0.85%.
The metal material surface treatment agent of the present invention may contain, in addition to the above components, one or a combination of more of other components such as a pigment, an aqueous lubricant, a resin hardening component, a plasticizer, a water-soluble solvent, an antifoaming agent, an antifungal agent, a coloring agent, and a wettability improver that is useful for uniform coating, if necessary, or these components (components) may be added additionally at the time of production.
The solid content of the surface treatment agent for a metal material of the present invention is not particularly limited as long as the effect of the present invention can be achieved, but is preferably in the range of 0.5 to 45.0 mass%.
The method for producing the metal material surface treatment agent of the present invention is not particularly limited, and for example, it can be produced by compounding a silane (K) -modified filler (a) containing an anionic functional group, a polysiloxane polymer (C), a fluorine-containing compound (D), a vanadium compound (E), and a silicon-modified polyurethane (F) in order in water or a mixed liquid medium of water and an organic solvent, and further compounding other components as needed. Or the compounding sequence can be properly changed according to the needs, or a plurality of components can be premixed and then compounded. In addition, the components can be compounded or mixed after being heated as required, or the components can be compounded or mixed for multiple times. The liquid medium may be water alone or a mixture of water and a water-miscible organic solvent. The water-miscible organic solvent is not particularly limited as long as it is miscible with water and can be used in the present invention, and examples thereof include ketone solvents such as acetone and methyl ethyl ketone; amide solvents such as N, N-dimethylformamide and N, N-dimethylacetamide; alcohol solvents such as methanol, ethanol, and isopropyl alcohol; ether solvents such as ethylene glycol monobutyl ether and ethylene glycol hexyl ether; pyrrolidone-based solvents such as N-methylpyrrolidone and N-ethyl-2-pyrrolidone. The organic solvent miscible with water may be one of the organic solvents mixed with water, or two or more of the organic solvents mixed with water. The mass ratio of water in the mixture is usually 25% or more, more preferably 50% or more, most preferably 60% or more, particularly preferably 80% or more.
The method for surface treatment of a metal material of the present invention comprises coating a surface of a metal material with an upper metal material surface treatment agent and drying the coating to produce a metal material having a film (coating or skin).
In the description of the present invention, the above-mentioned metal materials include, but are not limited to, copper alloy, aluminum alloy, and stainless steel. Among them, copper alloys such as: h59 brass, T1 red copper, HPb59-1 lead copper, cupronickel, bronze, and the like. Examples of the aluminum alloy include: 2011 copper aluminum alloy, 5052 magnesium aluminum alloy, 7075 zinc aluminum alloy, manganese aluminum alloy, silicon aluminum alloy, and the like. Examples of the stainless steel include 13-chromium stainless steel of martensite, 18-chromium stainless steel of ferrite, 18-chromium-8-nickel stainless steel of austenite, duplex stainless steel, and PH stainless steel. The shape of the metal material is not particularly limited, and may be a shaped object such as a metal plate structure, for example.
In the present invention, before the surface of the metal material is coated with the above-mentioned surface treatment agent for a stainless steel material, it is possible to have 1 or more layers of other coating films (coatings) on a part or all of the surface thereof. The other coating may be a passivation coating or a coating formed by an undercoating treatment mentioned below.
In the description of the present invention, before the surface of the metal material is coated with the above-mentioned metal material surface treatment agent, the surface of the metal material may be pre-cleaned by a suitable combination of degreasing agent, alkali cleaning, hot water washing, acid cleaning, solvent cleaning, etc., or may not be pre-cleaned. In addition, if the metal material is preliminarily cleaned, the surface of the metal material may be washed with water and dried or may not be washed with water and dried before the surface treatment agent is applied after the preliminary cleaning.
The metal material may be subjected to an undercoating treatment before the surface of the metal material is coated with the surface treatment agent (after the above-mentioned preliminary cleaning is performed as necessary). The method of the undercoating treatment is not particularly limited, and examples thereof include a surface conditioning treatment in which a metal such as Fe, co, ni, cu, zn, mn, zr, ti, or V is attached, and a chemical conversion treatment such as phosphate-based or zirconium-based treatment. After the undercoating treatment, the material surface may be washed with water and dried so that the treatment liquid does not remain on the material surface. After the undercoating treatment, washing with water may not be carried out.
The surface treatment agent for a metal material may be applied to a part or the whole of the surface of the metal material. The method of coating the surface treatment agent for a metal material on the surface of a metal material is not particularly limited, and examples thereof include roll coating, dipping, shower coating, and bar coating. The temperature of the surface treatment agent at the time of coating is not particularly limited, but is more preferably 5 to 40 ℃, and most preferably 10 to 30 ℃.
The drying method after coating is not particularly limited, and other than natural drying, for example, heating and drying methods such as a blower, a hot air oven, a high-frequency induction heating oven, and an infrared oven can be cited. The drying Temperature is not particularly limited, but it is preferable that the maximum Temperature is in the range of 60 to 200 ℃.
The amount of the coating formed by the above-mentioned step is not particularly limited, but is preferably 0.5 to 50.0g/m 2 More preferably 2.0 to 40.0g/m 2 。
In the description of the present invention, "water" includes, but is not limited to, deionized water and distilled water.
In the description of the present invention, "plural" means two or more.
The invention will be further illustrated with reference to the following specific examples. The specific embodiment is implemented on the premise of the technical scheme of the invention, and a detailed implementation mode and an operation process are given. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental methods in the following examples, which are not specified under specific conditions, are generally carried out under conventional conditions. Unless otherwise indicated, ratios and percentages are by weight.
Preparation of surface treating agent
The components were mixed in water in accordance with the components and their contents shown in Table 1, to thereby obtain the surface treatment agents for metal materials of examples 1 to 6 and comparative examples 1 to 5. In the composition of the surface treating agent, the remainder of the components (A), (C), (D), (E) and (F) is water. In the examples and comparative examples, the solid concentration of the surface treatment agent was about 8 mass%.
Preparation of silane K1 containing anionic functional groups:
in a triangular flask, 1mol1,3,5, 7-tetravinyltetramethylcyclotetrasilane (D4H) and 4mol α -methylstyrene (AMS) were added together with a HIPEC 13100 platinum catalyst prepared by Johnson Matthey, and reacted under a nitrogen protection condition of 115 ℃ to obtain an intermediate, which was reacted with chlorosulfonic acid dissolved in dichloromethane at a molar ratio of 1.
Preparation of silane K2 containing anionic functional groups:
5g of the final product K1 of example 1 and 250g of octamethylcyclotetrasiloxane (octamethylcyclotetrasiloxane) (Konghai chemical Co., ltd.) and 5.2g of 1,3-divinyl-1, 3-tetramethyldisiloxane (1, 3-divinyl-1, 3-tetramethyldisiloxane) were reacted, and after completion of the reaction, sodium carbonate was added to neutralize, thereby obtaining a final product K2.
The symbols in table 1 represent the following meanings:
a1:5g of nano boron nitride (Suzhou Nanpu Tree materials science and technology Co., ltd.), 3g of nano graphene (Chinese academy of sciences organic chemistry Co., ltd.), 2g of K1 and 90g of deionized water were mixed at 2000rpm to obtain a product with a solid content of 10 mass%. [ TK)/(TA) ] =20%
A2:400g of graphite (HT D50, qingdao Huatai sealing science and technology Limited company) with the particle size of 400nm, 99g of silicon nitride (ZH-Si 3N4-01, zhonghang nanotechnology development Limited company, hefei), 1g of K2 and 5750g of deionized water are mixed under the condition of 2000rpm to obtain a product with the solid content of 8 mass percent. [ TK)/(TA) ] =0.2%.
C1:1mol of hexamethylenediamine and 2mol of 3-glycidyloxypropyltriethoxysilane are reacted in ethanol to obtain the final product, and then deionized water is added to adjust the solids content to 5% by mass.
C2:1mol of epoxy resin (ADEKA EP-4100) and 2mol of 3-aminopropyltriethoxysilane are reacted in N-methyl-2-pyrrolidone to obtain the final product. Then, deionized water was added to adjust the solid content to 5% by mass.
D1: and (4) ammonium fluoride.
D2: ammonium fluorozirconate.
E1: sodium metavanadate.
E2: LPV1 (NVC = 16.6%) manufactured by shanghai brazier new material science and technology development limited.
F1: WHW-822 (NVC = 35%) manufactured by DIC corporation.
F2: SU-189 (NVC = 26%) manufactured by Shanghai Bibai New Material science and technology development Co.
Metal material
The metal material adopts aluminum magnesium alloy 5052, and the plate thickness is 1.0mm.
Production of metal material having coating film:
the surface of the aluminum plate was degreased using a fine degreaser FC-315 made of decamba (concentration 2%, 60 ℃, sprayed for 2 minutes), washed with water, and dried. Then, the surface treating agent for each stainless steel material is added at a ratio of 2.0 to 10.0g/m 2 The coating amount of the coating was applied to one surface of an aluminum plate by bar coating, and the maximum reaching plate Temperature (PMT: peak Metal Temperature) was 160 ℃, followed by drying, thereby obtaining test materials 1 to 11.
Evaluation test of Performance of Metal Material having coating film
The following performance evaluation tests were performed on the test materials 1 to 11 (corresponding to examples 1 to 6 and comparative examples 1 to 5, respectively). The evaluation results are shown in table 2. As for the evaluation criteria, ". Smallcircle" and ". Circleincircle" mean that the performance is satisfied in practice.
1) Adhesion property
The surface of the film of the test material was cut at a cutter interval of 1mm in the horizontal and vertical directions to form 100-grid-shaped cuts (vertical × horizontal =10 × 10). Then, the notched portion was subjected to 8mm extrusion processing using a cup drawing tester. The tape was attached to the processing portion and then peeled off. The number of peel lattices of the film was visually measured, the peel area ratio (number of peel lattices) was calculated, and the adhesion was evaluated according to the following criteria.
Evaluation criteria:
very good: the area ratio is less than or equal to 5%
O: the area ratio is more than 5 percent and less than or equal to 10 percent
And (delta): the area ratio is more than 10 percent and less than or equal to 20 percent
X: the area ratio is more than 20 percent
2) Heat resistance
After the test material was heated at 300 ℃ for 1hr, the surface of the film was cut at a cutter interval of 1mm in the transverse and longitudinal directions to form 100-lattice-like cuts (longitudinal × transverse =10 × 10). Then, the cut portion was subjected to 8mm extrusion processing using a cup-shaped testing machine. The tape is attached to the processing portion and then peeled off. The number of peel lattices of the film was visually measured, the peel area ratio (number of peel lattices) was calculated, and the adhesion was evaluated according to the following criteria.
Evaluation criteria:
very good: the area ratio is less than or equal to 5%
O: the area ratio is more than 5 percent and less than or equal to 10 percent
And (delta): the area ratio is more than 10 percent and less than or equal to 20 percent
X: the area ratio is more than 20 percent
3) Coefficient of thermal conductivity
The heat conductivity of the test materials was measured by GB/T10294-2008 method.
Evaluation criteria:
excellent: thermal conductivity ≧ 3.0W/(m.k)
O: 3W/(m.k) < thermal conductivity ≦ 2.5W/(m.k)
And (delta): 2.5W/(m.k) < thermal conductivity ≦ 2.0W/(m.k)
X: thermal conductivity coefficient < 2.0W/(m.k)
TABLE 2 evaluation of the properties of the metallic material surface treating agents of examples 1 to 6 and comparative examples 1 to 5
| Adhesion property | Heat resistance | Coefficient of thermal conductivity | ||
| Test Material 1 | Example 1 | ◎ | ○ | ○ |
| Test Material 2 | Example 2 | ○ | ○ | ○ |
| Test Material 3 | Example 3 | ◎ | ○ | ○ |
| Test Material 4 | Example 4 | ○ | ◎ | ○ |
| Test Material 5 | Example 5 | ○ | ○ | ◎ |
| Test Material 6 | Example 6 | ○ | ◎ | ◎ |
| Test Material 7 | Comparative example 1 | ◎ | ○ | × |
| Test Material 8 | Comparative example 2 | ○ | × | ○ |
| Test Material 9 | Comparative example 3 | × | ○ | ○ |
| Test material 10 | Comparative example 4 | × | × | ○ |
| Test material 11 | Comparative example 5 | × | ○ | ◎ |
In comparative example 1, the content of component A was small as compared with that in example 1, and the thermal conductivity was poor. In comparative example 2, the amount of component A was large, the amount of component C was small, and the heat resistance was poor. Comparative example 3, which contained no component D, exhibited poor adhesion to the substrate. Comparative example 4 has poor adhesion to the substrate and poor heat resistance compared to example 1 without component E. Comparative example 5, which contained no component F, exhibited poor adhesion to the substrate.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not intended to limit the scope of the present invention. All simple and equivalent changes and modifications made according to the claims and the content of the specification of the present application fall within the scope of the claims of the present patent application. The invention has not been described in detail in order to avoid obscuring the invention.
Claims (10)
1. The surface treatment agent for the metal material is characterized by comprising the following components in parts by weight:
2. the surface treatment agent for metallic materials according to claim 1, wherein the silane (K) modified filler (a) having an anionic functional group has one or more characteristics selected from the group consisting of:
the filler (A) is selected from one or more of graphene, graphite fiber, metal boride, metal carbon compound, nitride and metal silicide, and/or
The silane (K) containing anionic functional groups has the structural formula I: tx + My - (SiR 1 R 2 R 3 ) n ,
Wherein x is 1-2, y is 1-3, n is 1-50,
R 1 、R 2 、R 3 each independently selected from alkyl, alicyclic group or aromatic group with 1-20 carbon atoms;
t is hydrogen or a cationic functional group, wherein the cationic functional group is a group IA element ion, a group IIA element ion, a rare earth element ion, a quaternary ammonium salt or a cationic polymer;
m is sulfonic acid group (-SO) 3 - ) Sulfuric acid anion group (-OSO) 3 - ) Carboxyl (-COO) - ) Organic phosphoric acid group (-PO) 3 2- ) Phosphate group (-OPO) 3 2- ) And/or
The weight content of the silane (K) containing the anionic functional group in the silane (K) modified filler (A) containing the anionic functional group is 0.2 to 20.0 percent.
3. The surface treating agent for metallic materials according to claim 2, characterized in that the method for preparing the silane (K) containing an anionic functional group comprises the steps of:
1,3,5,7-tetravinyl tetramethyl cyclo tetrasilane, alpha-methyl styrene (AMS) and HISPEC13100 platinum catalyst prepared by Johnson Matthey react under the protection of nitrogen at 100-130 ℃ to obtain an intermediate, the intermediate reacts with chlorosulfonic acid to obtain silane containing anionic functional groups,
wherein the molar ratio of 1,3,5, 7-tetravinyltetramethylcyclotetrasilane to alpha-methylstyrene is 1:3 to 5, and
wherein the molar ratio of the intermediate to chlorosulfonic acid is 1.
4. The surface treating agent for metallic materials according to claim 1, wherein the molecular structure of the polysiloxane polymer (C) comprises SiR 4 R 5 R 6 Structure (II) wherein R 4 、R 5 、R 6 Each independently selected from alkyl groups having 1 to 4 carbon atoms or hydroxyl groups, provided that R 4 、R 5 、R 6 Not simultaneously being hydroxyl.
5. The metallic material surface treatment agent according to claim 1, wherein the fluorine-containing compound (D) is selected from a combination of one or more of titanium-containing fluoride, zirconium-containing fluoride, silicon-containing fluoride, hydrofluoric acid, ammonium fluoride and ammonium bifluoride.
Preferably, the titanium-containing fluoride is selected from one or more of fluotitanic acid, ammonium fluotitanate, potassium fluotitanate and sodium fluotitanate, and/or
Preferably, the zirconium-containing fluoride is selected from one or more of fluorozirconic acid, ammonium fluorozirconate, potassium fluorozirconate and sodium fluorozirconate, and/or
Preferably, the silicon-containing fluoride is selected from one or more of fluorosilicic acid, ammonium fluorosilicate, potassium fluorosilicate and sodium fluorosilicate.
6. The metallic material surface treatment agent according to claim 1, wherein the vanadium compound (E) is selected from one or more of a vanadium alkoxide, a vanadium-containing chelate complex, an inorganic salt of vanadium, an organic salt of vanadium, and an organic vanadium compound and a vanadium oxide in combination,
preferably, the vanadium compound (E) is selected from the group consisting of vanadium pentoxide, metavanadate, ammonium metavanadate, sodium metavanadate, potassium metavanadate, vanadium oxytrichloride, vanadium trioxide, vanadium dioxide, vanadyl sulfate, vanadyl acetylacetonate, vanadium trichloride and a combination of one or more of phosphomolybdovanadate.
7. The surface treatment agent for metallic materials according to claim 1, wherein the silicon-modified polyurethane (F) is a silicon-modified polyurethane (F) having a polysiloxane structure of 30% or more of the total amount.
8. The metallic material surface treatment agent according to any one of claims 1 to 6, further comprising a combination of one or more of the following components:
water, an organic solvent, a pigment, a water-based lubricant, a resin hardening component, a plasticizer, a water-soluble solvent, a defoaming agent, an antibacterial and antifungal agent, and a coloring agent.
9. The method for producing the surface treatment agent for metallic materials according to any one of claims 1 to 6, characterized by comprising: adding silane (K) modified filler (A) containing anionic functional groups, polysiloxane polymer (C), fluorine-containing compound (D), vanadium compound (E) and silicon modified polyurethane (F) into water or a mixture of water and an organic solvent, and uniformly mixing,
the organic solvent is mutually soluble with water, and the mass content of water in the mixture of the water and the organic solvent is not less than 25%.
10. A method for treating the surface of a metal material, which comprises applying the surface treating agent of any one of claims 1 to 7 on the surface of the metal material, drying and forming a film, wherein the film forming temperature (PMT) is controlled to be 60 to 200 ℃,
the metal material is copper, copper alloy, aluminum alloy or stainless steel.
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