JPH0319319B2 - - Google Patents
Info
- Publication number
- JPH0319319B2 JPH0319319B2 JP27352386A JP27352386A JPH0319319B2 JP H0319319 B2 JPH0319319 B2 JP H0319319B2 JP 27352386 A JP27352386 A JP 27352386A JP 27352386 A JP27352386 A JP 27352386A JP H0319319 B2 JPH0319319 B2 JP H0319319B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- organic polymer
- formula
- soluble organic
- additive according
- 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.)
- Expired
Links
- 229920000620 organic polymer Polymers 0.000 claims description 44
- 239000000654 additive Substances 0.000 claims description 34
- 230000000996 additive effect Effects 0.000 claims description 29
- XLLXMBCBJGATSP-UHFFFAOYSA-N 2-phenylethenol Chemical compound OC=CC1=CC=CC=C1 XLLXMBCBJGATSP-UHFFFAOYSA-N 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- JESXATFQYMPTNL-UHFFFAOYSA-N mono-hydroxyphenyl-ethylene Natural products OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 238000009713 electroplating Methods 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- -1 halogen ions Chemical class 0.000 claims description 9
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 150000002892 organic cations Chemical class 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims 1
- 125000002091 cationic group Chemical group 0.000 claims 1
- 238000007747 plating Methods 0.000 description 50
- 238000011282 treatment Methods 0.000 description 31
- 239000003973 paint Substances 0.000 description 23
- 230000007797 corrosion Effects 0.000 description 20
- 238000005260 corrosion Methods 0.000 description 20
- 239000000126 substance Substances 0.000 description 15
- 238000000576 coating method Methods 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 229910000831 Steel Inorganic materials 0.000 description 10
- 239000010959 steel Substances 0.000 description 10
- 238000010422 painting Methods 0.000 description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- 229910019142 PO4 Inorganic materials 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000010452 phosphate Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000002585 base Substances 0.000 description 6
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000007769 metal material Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000005507 spraying Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- 229910001297 Zn alloy Inorganic materials 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000004381 surface treatment Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- WUQYBSRMWWRFQH-UHFFFAOYSA-N 2-prop-1-en-2-ylphenol Chemical compound CC(=C)C1=CC=CC=C1O WUQYBSRMWWRFQH-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 125000004103 aminoalkyl group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000005422 blasting Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 125000005358 mercaptoalkyl group Chemical group 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000005488 sandblasting Methods 0.000 description 2
- 238000013341 scale-up Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- 125000001174 sulfone group Chemical group 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- YGBVAGIVGBLKFE-UHFFFAOYSA-N 2-phenylbut-1-en-1-ol Chemical compound CCC(=CO)C1=CC=CC=C1 YGBVAGIVGBLKFE-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- MKHXOKALQIHXPI-UHFFFAOYSA-N 2-phenylprop-1-en-1-ol Chemical compound OC=C(C)C1=CC=CC=C1 MKHXOKALQIHXPI-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 238000005654 Michaelis-Arbuzov synthesis reaction Methods 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- VNQABZCSYCTZMS-UHFFFAOYSA-N Orthoform Chemical compound COC(=O)C1=CC=C(O)C(N)=C1 VNQABZCSYCTZMS-UHFFFAOYSA-N 0.000 description 1
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- MOFCYHDQWIZKMY-UHFFFAOYSA-N chloromethylphosphonic acid Chemical compound OP(O)(=O)CCl MOFCYHDQWIZKMY-UHFFFAOYSA-N 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 125000005265 dialkylamine group Chemical group 0.000 description 1
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- PARDSSZKOJRLBK-UHFFFAOYSA-N ethyl dihydrogen phosphate prop-2-enoic acid Chemical compound C(C=C)(=O)O.C(C)OP(O)(=O)O PARDSSZKOJRLBK-UHFFFAOYSA-N 0.000 description 1
- 238000009778 extrusion testing Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- YOYLLRBMGQRFTN-SMCOLXIQSA-N norbuprenorphine Chemical compound C([C@@H](NCC1)[C@]23CC[C@]4([C@H](C3)C(C)(O)C(C)(C)C)OC)C3=CC=C(O)C5=C3[C@@]21[C@H]4O5 YOYLLRBMGQRFTN-SMCOLXIQSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Inorganic materials O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- DXIGZHYPWYIZLM-UHFFFAOYSA-J tetrafluorozirconium;dihydrofluoride Chemical compound F.F.F[Zr](F)(F)F DXIGZHYPWYIZLM-UHFFFAOYSA-J 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229920003176 water-insoluble polymer Polymers 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
Description
〔産業上の利用分野〕
本発明は新規な電気めつき浴添加剤に係る。
更に詳しくは、塗料密着性、裸耐蝕性、塗装後
耐蝕性、溶接性、プレス加工性等の諸特性に優れ
た新規な有機高分子複合電気めつき皮膜を生成さ
せる電気めつき浴添加剤に関するものである。
〔従来の技術〕
従来、金属表面、特に鋼板表面に美観および耐
蝕性を付与するため亜鉛や亜鉛合金めつきが広く
行われている。なかでも最近自動車用鋼板は融雪
塩散布によつて自動車の使用環境が厳しい状況下
にあるため防錆対策からこの亜鉛系めつきが施さ
れる割合が急増している。これらのめつき金属材
は、耐蝕性の増加および装飾性付与等の目的か
ら、めつきの上に塗装して使用されることが多
い。ところが亜鉛および亜鉛合金めつき等の金属
めつき表面は一般に塗料密着性が悪いため塗装に
先立つて塗装下地処理が施されるのが普通であ
る。その方法は各種検討され実用化されており、
代表例としてはリン酸塩処理法やクロム酸溶液に
よるクロメート処理法などの化学的な処理（化成
処理）と、サンドブラスト、グリツドブラスト等
により表面に凹凸を付与する物理的処理等とがあ
る。これらの方法はいずれも有効接着表面積の増
加やアンカー効果を主に期待するもので、いわゆ
る表面形態のコントロール技術である。
また一方では塗装下地処理を必要としないめつ
き皮膜も検討されている。例えばめつき浴中に水
不溶性樹脂を分散して共析させる分散めつき方法
（米国特許第3434942号および同第3461044号）が
あり、この方法は樹脂複合により皮膜の塗料との
親和性の増加を期待したものである。
〔発明が解決しようとする問題点〕
しかるにリン酸塩処理やクロメート処理などの
化成処理は工程管理・公害防止上の点から問題が
多い。即ちリン酸塩処理は、亜鉛系めつき金属材
の塗装下地処理としては最も多く使用されている
が、工程の長さ（６〜９ステツプ）や浴管理の煩
雑さばかりではなく、大量に発生するスラツジや
廃液処理などの点で制約・問題が多い。一方クロ
メート処理はクロムの毒性および排水処理に難点
をもつばかりでなく、塗料密着性が必ずしも良好
でないという本質的欠点を有している。
またこのような化学的処理によつて被覆した無
機酸化物層は高度なプレス加工に耐えないという
欠点を有している。
サンドブラスト等による物理的処理はアンカー
効果を充分に発揮するまでの微細かつ複雑な凹凸
を広範囲にわたつて付与することが困難である。
水不溶性樹脂の分散めつき法は注目すべき技術
であるが、樹脂粒子の均一分散安定化が難しく、
スケールアツプが極めて困難、即ち大面積の鋼帯
に均質なめつきを施すのが難しい点や、塗料密着
性が必ずしも充分でない、プレス加工性が悪いな
ど物性の点でも問題が多い。
上述の如く、現行技術ではめつき性能、塗装下
地処理技術とも不完全でありながら、工業的ニー
ズとしては、特に自動車ボデイーに使用される防
錆鋼板には、近年耐久年数の増加から高度な塗料
密着性や防錆性に優れた防錆鋼板が強く求められ
ている。
〔問題点を解決するための手段〕
本発明は従来の電気めつき皮膜特に亜鉛系めつ
き皮膜、更には塗装下地処理のもつている欠点を
鑑み、塗装下地処理を施さなくとも充分塗料密着
性に優れ、かつ耐蝕性、溶接性、プレス加工性に
優れた高水準の多機能めつき皮膜を生成する電気
めつき浴添加剤の完成を意図したものである。即
ち、本発明は従来の合金元素の調整とか、化成処
理およびブラスト処理などの塗装前処理の改良と
いつた従来の発想から離れて、水溶性有機高分子
の基本骨格、極性基の種類と密度、分子量の作
用、およびめつき浴への添加量等に関し、電気め
つき浴添加剤について鋭意検討した結果、本発明
者らはある特定の化学構造を有する水溶性の有機
高分子を電気めつきに応用することにより、上記
目的を十分達成できることを見い出し、本発明の
めつき浴添加剤の完成に至つたのである。
即ち、本発明はヒドロキシスチレン系重合体、
またはこれらの誘導体からなる水溶性の有機高分
子の１種以上を主成分として含有し、塗料密着
性、耐蝕性等に優れた電気めつき皮膜を生成させ
る、電気めつき浴添加剤を提供するものである。
本発明の添加剤によると、有機高分子の基本骨
格（芳香環、水酸基）、極性基の種類（スルホン
基など）、分子量（1000〜100万）等の作用および
めつき浴への添加量とめつき条件とを選択するこ
とによつて、めつき結晶粒子径および形態のコン
トロール（微細化および凹凸化）を行い、接着有
効面積の増加を計り塗装下地表面に好適な表面と
することができる。
また、特定の有機高分子の適量と金属とを、分
子オーダーであるいは極めてミクロに複合化さ
せ、めつき表面の形態の効果に加えて更にめつき
表面と塗料との親和性、反応性（結合性）を高
め、また複合した有機高分子の作用によつて防錆
性、溶接性を高めることができる。
本発明に使用できるヒドロキシスチレン系有機
高分子としては、重量平均分子量が1000〜100万
の高分子であつて、分子量500単位当たりに少な
くとも１個以上の水酸基（−OH）を置換基とし
て有する芳香環を平均0.5個以上と水可溶性基と
を必須成分として有し、かつ芳香環と芳香環とを
結ぶ主鎖がＣ−Ｃ結合、エーテル結合（Ｃ−Ｏ−
Ｃ）のうちいずれか１種以上で構成される水溶性
有機高分子が挙げられる。
ここで芳香環と芳香環とを結ぶ主鎖のＣ−Ｃ結
合、Ｃ＝Ｃ結合、エーテル結合（Ｃ−Ｏ−Ｃ）の
概念の中にはポリ−ｐ−ヒドロキシスチレン、リ
グニンスルホン酸ソーダ、ニトロフミン酸などが
含まれる。但し縮合環（
[Industrial Field of Application] The present invention relates to a novel electroplating bath additive. More specifically, it relates to an electroplating bath additive that produces a novel organic polymer composite electroplated film with excellent properties such as paint adhesion, bare corrosion resistance, post-painting corrosion resistance, weldability, and press workability. It is something. [Prior Art] Conventionally, zinc or zinc alloy plating has been widely used to impart beauty and corrosion resistance to metal surfaces, particularly steel plate surfaces. In recent years, steel sheets for automobiles have been coated with zinc-based plating as a rust-preventing measure, as the environment in which automobiles are used has become harsher due to the application of snow-melting salt. These plated metal materials are often used by being coated on top of the plating for the purpose of increasing corrosion resistance and imparting decorative properties. However, metal-plated surfaces such as those plated with zinc or zinc alloy generally have poor paint adhesion, and therefore a surface treatment is usually applied prior to painting. Various methods have been studied and put into practical use.
Typical examples include chemical treatments (chemical conversion treatments) such as phosphate treatment and chromate treatment using a chromic acid solution, and physical treatments such as sandblasting, grid blasting, etc., which impart unevenness to the surface. All of these methods are mainly expected to increase the effective adhesive surface area and anchor effect, and are so-called surface morphology control techniques. On the other hand, plating films that do not require surface treatment for painting are also being considered. For example, there is a dispersion plating method (U.S. Pat. No. 3,434,942 and U.S. Pat. No. 3,461,044) in which a water-insoluble resin is dispersed and eutectoid in a plating bath. This is what I expected. [Problems to be Solved by the Invention] However, chemical conversion treatments such as phosphate treatment and chromate treatment have many problems in terms of process control and pollution prevention. In other words, phosphate treatment is the most commonly used base treatment for coating zinc-plated metal materials, but it is not only a long process (6 to 9 steps) and complicated bath management, but also a large amount of phosphate treatment. There are many restrictions and problems in terms of sludge and waste liquid treatment. On the other hand, chromate treatment not only has problems with chromium toxicity and drainage treatment, but also has the essential drawback that paint adhesion is not always good. Furthermore, the inorganic oxide layer coated by such chemical treatment has the disadvantage that it cannot withstand high-level press processing. Physical treatment such as sandblasting makes it difficult to provide fine and complex unevenness over a wide range to sufficiently exhibit the anchor effect. The dispersion plating method for water-insoluble resins is a noteworthy technology, but it is difficult to stabilize the uniform dispersion of resin particles.
It is extremely difficult to scale up, that is, it is difficult to uniformly plate a large area of steel strip, and there are many problems in terms of physical properties, such as insufficient paint adhesion and poor press workability. As mentioned above, although the plating performance and coating surface treatment technology are incomplete with the current technology, there are industrial needs, especially for rust-proof steel sheets used in automobile bodies, as the durability has increased in recent years. There is a strong demand for rust-proof steel sheets with excellent adhesion and rust-proofing properties. [Means for Solving the Problems] In view of the drawbacks of conventional electroplated films, particularly zinc-based plating films, and furthermore, the coating surface treatment, the present invention provides sufficient paint adhesion without the need for coating surface treatment. The objective is to complete an electroplating bath additive that produces a high-level multifunctional plating film with excellent corrosion resistance, weldability, and press workability. That is, the present invention departs from conventional ideas such as adjusting alloying elements and improving pre-painting treatments such as chemical conversion treatment and blasting, and instead focuses on the basic skeleton of water-soluble organic polymers, the type and density of polar groups, etc. As a result of extensive research into electroplating bath additives, including the effect of molecular weight and the amount added to the plating bath, the present inventors have developed a method for electroplating water-soluble organic polymers with a specific chemical structure. They have discovered that the above objectives can be fully achieved by applying the present invention to the plating bath additive of the present invention. That is, the present invention provides a hydroxystyrene polymer,
Or to provide an electroplating bath additive containing as a main component one or more water-soluble organic polymers made of these derivatives, which produces an electroplating film with excellent paint adhesion, corrosion resistance, etc. It is something. According to the additive of the present invention, the effects of the basic skeleton of the organic polymer (aromatic ring, hydroxyl group), type of polar group (sulfone group, etc.), molecular weight (10 million to 1 million), etc., and the amount added to the plating bath are determined. By selecting the plating conditions, the diameter and morphology of the plating crystal particles can be controlled (refined and uneven), and the effective adhesion area can be increased to create a surface suitable for the base surface to be coated. In addition, by combining an appropriate amount of a specific organic polymer with a metal on a molecular order or on an extremely microscopic scale, in addition to the effect of the morphology of the plated surface, we can also improve the affinity and reactivity (bond Furthermore, due to the action of the composite organic polymer, rust prevention and weldability can be improved. The hydroxystyrene organic polymer that can be used in the present invention is an aromatic polymer having a weight average molecular weight of 10 million to 1 million, and having at least one hydroxyl group (-OH) as a substituent per 500 units of molecular weight. It has an average of 0.5 or more rings and a water-soluble group as essential components, and the main chain connecting the aromatic rings is a C-C bond, an ether bond (C-O-
Examples include water-soluble organic polymers composed of one or more of C). Here, the concepts of C-C bonds, C=C bonds, and ether bonds (C-O-C) in the main chain connecting aromatic rings include poly-p-hydroxystyrene, sodium ligninsulfonate, Contains nitrofumic acid. However, fused rings (
【式】など）
をもつて主鎖内に上記結合が存在するとは本発明
では見做さない。またこれら有機高分子の側鎖に
は上述の官能基の他に、Cl、Brなどのハロゲン
基、ニトリル基、ニトロ基、エステル基など他の
官能基を含んでいてもよい。
本発明は上記の条件を満たす水溶性有機高分子
の中で、次の一般式(A)
（式中；ｍ≧０、ｎ≧３でそれぞれ一般式(A)の
有機高分子の重量平均分子量が100万になるまで
の任意の数、
；０≦ｋ≦２，
；０≦ｐ≦２，
；ただしｋ＋ｐ＋ｍ＞０，
；R1〜R3はＨまたは炭素数１〜５のアルキル
基、
；Ｘは重合性のビニル系単量体、
；Ｙ，Ｚは同種または異種であり、かつ
−SO3M，−CH2−SO3M，−Y1，−OCH3，[Formula], etc.) The present invention does not consider that the above bond exists in the main chain. In addition to the above-mentioned functional groups, the side chains of these organic polymers may contain other functional groups such as halogen groups such as Cl and Br, nitrile groups, nitro groups, and ester groups. The present invention uses the following general formula (A) as a water-soluble organic polymer that satisfies the above conditions. (In the formula; m≧0, n≧3, respectively, an arbitrary number until the weight average molecular weight of the organic polymer of general formula (A) reaches 1 million, ;0≦k≦2, ;0≦p≦2 , ; However, k+p+m>0, ; R 1 to R 3 are H or an alkyl group having 1 to 5 carbon atoms, ; X is a polymerizable vinyl monomer, ; Y and Z are the same or different, and - SO 3 M, −CH 2 −SO 3 M, −Y 1 , −OCH 3 ,
【式】【formula】
【式】【formula】
【式】−（CH2）tY4，
−CH2OH
から選ばれるものであつて、〔式中
；ＭはＨ、アルカリ金属、アルカリ土類金属、
またはアミン類などの有機カチオン、
；Y1，Y4はハロゲン
；Y2-〜Y3-はハロゲイオン、有機酸アニオン、
無機酸アニオンなどの対イオン
；ＷはＳまたは０
；R4〜R6は同種または異種であつて、直鎖ま
たは分岐鎖アルキル基あるいはヒドロキシア
ルキル基等のアルキル基誘導体または芳香族
基、またはR4とR5はＮ基とで環を形成して
いてもかまわない。さらにR6はＨをとり得
る。
；R7〜R13は同種または異種であつて、直鎖ま
たは分岐鎖アルキル基、あるいはヒドロキシ
アルキル基等のアルキル誘導体基、芳香族
基、またはＨ
；ｑ，ｓ，ｔ，ｕは０または１
；ｒは０，１または２をを示す〕）
で表される水溶性有機高分子をめつき浴添加剤と
して用いれば、特に優れた塗料密着性、耐蝕性等
に優れる複合めつき皮膜が得られることを見い出
したものである。
上記一般式(A)において、ｍ，ｎ，ｋ，ｐはそれ
ぞれ整数とは規定せず、ある一定の範囲の任意の
数（実数）である。重合体を構成する単量体につ
いて考えるならば、ｋ，ｐは当然整数であり、構
成単位のブロツクごとに考えるならば、ｍは整数
であり、そして分子ごとに考えるならば、ｎは整
数である。しかしながら重合体はその本質におい
て、混合物であり、そして重合体の性質はその混
合物の性質としてとらえる方が、その個々の構成
単位を問題にするよりも正しい。従つて、本発明
において、式(A)は平均組成として表示してある。
上記一般式(A)で表されるヒドロキシスチレン系
有機高分子は、一般式(A)においてＹまたはＺで表
されるような置換基を有するかあるいは有しない
ところの、ヒドロキシスチレン、イソプロペニル
フエノール（ヒドロキシ−α−メチルスチレン）
あるいはヒドロキシ−α−エチルスチレン等の単
独重合体、これら同志の共重合体あるいはこれら
のヒドロキシスチレン系単量体と他の重合性のビ
ニル系単量体（Ｘ）との共重合体であり得る。重
合単位のヒドロキシスチレンあるいはイソプロベ
ニルフエノールなどはオルソ体、メタ体、パラ体
あるいはこれらの混合物であつてもよいが、パラ
体あるいはメタ体が好ましい。
また共重合体である場合の他のビニル系単量体
の例としては、無水マレイン酸、マレイン酸、ア
クリル酸、メチルメタアクリレート、メタクリル
酸、グリシジルメタクリレート、ヒドロキシエチ
ルメタクリレート、イタコン酸、アリルスルホン
酸、、スチレンスルホン酸、アクリルギンエチル
フオスフエート、アクリルアミド、２−アクリル
アミド−２−メチルプロパンスルホン酸、アクリ
ルニトリル、マレイミド、ビニルピリジン、アク
リル酸エステル、メタクリル酸エステル、フマル
酸エステルあるいは各種有機酸のビニルエステル
などが挙げられる。またこの場合におけるヒドロ
キシスチレン単位あるいはイソプロペニルフエノ
ール単位などのヒドロキシスチレン系単位と他の
ビニル系単量体との割合はモル比で１／10〜20／
１までが適当である。またヒドロキシスチレン系
単位の置換基−SO3Mまたは−CH2−SO3Mにお
けるＭのアルカリ金属またはアルカリ土類金属と
してはLi，Na，Ｋ，Mg，Ca，Sr，Ba等が適当
である。スルホン基の導入は発煙硫酸または無水
硫酸などをスルホン化剤として用いる通常のスル
ホン化法により達成できる。またヒドロキシスチ
レン系単位
の置換基[Formula] -(CH 2 )tY 4 , -CH 2 OH, [In the formula; M is H, an alkali metal, an alkaline earth metal,
or organic cations such as amines; Y 1 and Y 4 are halogens; Y 2- to Y 3- are halogen ions, organic acid anions,
Counter ion such as an inorganic acid anion; W is S or 0; R 4 to R 6 are the same or different, and are an alkyl group derivative such as a straight or branched alkyl group or a hydroxyalkyl group, or an aromatic group, or R 4 and R 5 may form a ring with the N group. Furthermore, R 6 can be H. ; R 7 to R 13 are the same or different and are linear or branched alkyl groups, alkyl derivative groups such as hydroxyalkyl groups, aromatic groups, or H; q, s, t, and u are 0 or 1; ; r represents 0, 1 or 2]) If a water-soluble organic polymer represented by This is what we discovered. In the above general formula (A), m, n, k, and p are not defined as integers, but are arbitrary numbers (real numbers) within a certain range. If we consider the monomers that make up the polymer, k and p are naturally integers; if we consider each block of constituent units, m is an integer; and if we consider each molecule, n is an integer. be. However, a polymer is essentially a mixture, and it is more accurate to view the properties of a polymer as a property of the mixture than to consider its individual constituent units. Therefore, in the present invention, formula (A) is expressed as an average composition. The hydroxystyrene organic polymer represented by the above general formula (A) is hydroxystyrene, isopropenylphenol, which has or does not have a substituent represented by Y or Z in the general formula (A). (Hydroxy-α-methylstyrene)
Alternatively, it may be a homopolymer of hydroxy-α-ethylstyrene, a copolymer of these, or a copolymer of these hydroxystyrene monomers and another polymerizable vinyl monomer (X). . The polymerized units such as hydroxystyrene or isoprobenylphenol may be in the ortho form, the meta form, the para form, or a mixture thereof, but the para form or the meta form is preferable. Examples of other vinyl monomers in the form of copolymers include maleic anhydride, maleic acid, acrylic acid, methyl methacrylate, methacrylic acid, glycidyl methacrylate, hydroxyethyl methacrylate, itaconic acid, and allyl sulfonic acid. , styrene sulfonic acid, acrylic acid ethyl phosphate, acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, acrylonitrile, maleimide, vinylpyridine, acrylic ester, methacrylic ester, fumaric ester or various organic acids. Examples include vinyl ester. In this case, the molar ratio of hydroxystyrene units such as hydroxystyrene units or isopropenylphenol units to other vinyl monomers is 1/10 to 20/
Up to 1 is appropriate. In addition, suitable alkali metals or alkaline earth metals for M in the substituent -SO 3 M or -CH 2 -SO 3 M of the hydroxystyrene unit include Li, Na, K, Mg, Ca, Sr, Ba, etc. . Introduction of a sulfone group can be achieved by a conventional sulfonation method using fuming sulfuric acid or sulfuric anhydride as a sulfonation agent. Also, substituents of hydroxystyrene units
【式】あるいは[Formula] or
【式】
におけるR4〜R6は同種または異種であつて、炭
素数１〜36の直鎖または分岐鎖アルキル基、ある
いはヒドロキシアルキル基、アミノアルキル基、
ホスホアルキル基、メルカプトアルキル基等のア
ルキル誘導体基、または炭素数１〜16の直鎖、分
岐鎖アルキル基で置換されたベンジル基等の芳香
族基等の中から選択されるもので、前記化合物(A)
が水溶性でなくなるまでの炭素鎖を有するもので
ある。またR4とR5は環を形成していてもかまわ
ない。従つて好ましくは、直鎖または分岐鎖アル
キル基、ヒドロキシアルキル基、あるいは炭素数
１〜５の直鎖または分岐鎖アルキル基で置換され
た芳香族基が挙げられる。上記第３級アミノ基の
導入は、例えばジアルキルアミンとホルムアルデ
ヒドとを用いるマンニツヒ反応により容易に
R 4 to R 6 in [Formula] are the same or different, and each represents a straight or branched alkyl group having 1 to 36 carbon atoms, a hydroxyalkyl group, an aminoalkyl group,
It is selected from alkyl derivative groups such as phosphoalkyl groups and mercaptoalkyl groups, or aromatic groups such as benzyl groups substituted with linear or branched alkyl groups having 1 to 16 carbon atoms, and the above-mentioned compounds (A)
has a carbon chain that is not water-soluble. Further, R 4 and R 5 may form a ring. Therefore, preferable examples include straight-chain or branched-chain alkyl groups, hydroxyalkyl groups, or aromatic groups substituted with straight-chain or branched-chain alkyl groups having 1 to 5 carbon atoms. The above-mentioned tertiary amino group can be easily introduced by, for example, Mannitz reaction using dialkylamine and formaldehyde.
【式】が得られる。
また水溶性を向上させるためにはアミン部分を
中和する有機または無機酸が使用される。この目
的に有用な酸は酢酸、クエン酸、シユウ酸、アス
コルビン酸、フエニルホスホン酸、クロルメチル
ホスホン酸、モノ、ジ、およびトリクロル酢酸、
トリフルオロ酢酸、硫酸、リン酸、塩酸、ホウ
酸、硝酸、沸化水素酸、ヘキサフルオロケイ酸、
ヘキサフルオロチタン酸、ヘキサフルオロジルコ
ニウム酸が挙げられる。これらを単独あるいは混
合して用いてもよい。
第４級アンモニウム塩基の導入は、例えば上記
第３級アミノ化物に対するハロゲン化アルキルに
よるメンシユトキン反応により容易に[Formula] is obtained. Furthermore, in order to improve water solubility, an organic or inorganic acid that neutralizes the amine moiety is used. Acids useful for this purpose are acetic acid, citric acid, oxalic acid, ascorbic acid, phenylphosphonic acid, chloromethylphosphonic acid, mono-, di-, and trichloroacetic acid,
Trifluoroacetic acid, sulfuric acid, phosphoric acid, hydrochloric acid, boric acid, nitric acid, hydrofluoric acid, hexafluorosilicic acid,
Examples include hexafluorotitanic acid and hexafluorozirconic acid. These may be used alone or in combination. The introduction of a quaternary ammonium base can be easily carried out, for example, by the mensyutkin reaction with an alkyl halide on the above-mentioned tertiary aminated product.
【式】が得られる。
またヒドロキシスチレン系単位の置換基
におけるR7〜R13は同種または異種であつて、Ｈ
又は炭素数１〜36の直鎖または分岐鎖アルキル基
あるいはヒドロキシアルキル基、アミノアルキル
基、メルカプトアルキル基、ホスホアルキル基等
のアルキル誘導体基、または炭素数１〜16の直鎖
または分岐鎖アルキル基で置換されたフエニル基
の芳香族基等の中から選択されるものであつて、
前記化合物(A)が水溶性でなくなるまでの炭素鎖長
さを有するものである。従つて好ましくは炭素数
１〜８の直鎖または分岐鎖アルキル基、ヒドロキ
シアルキル基、あるいは炭素数１〜５の直鎖また
は分岐鎖アルキル基で置換された芳香族基が挙げ
られる。式（Ｄ）で表されるヒドロキシスチレン
系重合体は例えば特開昭53−47489号公報に開示
されているように、ヒドロキシスチレン系重合体
をまずハロゲ化ン化またはハロメチル化し、それ
に３価のリン化合物を反応（アルブゾフ反応）さ
せ、ついでそれを熱転位させることによつて得ら
れる。式(C)で表されるものは、例えば特開昭53−
71190号公報に開示されているように、ヒドロキ
シスチレン系重合体をメチロール化した後にリン
酸またはリン酸エステル基導入体と反応させるこ
とによつて得られる。また置換基に[Formula] is obtained. Also, substituents of hydroxystyrene units R 7 to R 13 are the same or different, and H
or a straight chain or branched alkyl group having 1 to 36 carbon atoms, or an alkyl derivative group such as a hydroxyalkyl group, aminoalkyl group, mercaptoalkyl group, or phosphoalkyl group, or a straight chain or branched alkyl group having 1 to 16 carbon atoms. selected from aromatic groups such as phenyl groups substituted with
The carbon chain length is such that the compound (A) is no longer water-soluble. Therefore, preferable examples include a straight chain or branched alkyl group having 1 to 8 carbon atoms, a hydroxyalkyl group, or an aromatic group substituted with a straight chain or branched alkyl group having 1 to 5 carbon atoms. The hydroxystyrene polymer represented by formula (D) is obtained by first halogenating or halomethylating the hydroxystyrene polymer, and then adding a trivalent It is obtained by reacting a phosphorus compound (Arbuzov reaction) and then subjecting it to thermal rearrangement. For example, the formula (C) is
As disclosed in Japanese Patent No. 71190, it can be obtained by methylolating a hydroxystyrene polymer and then reacting it with a phosphoric acid or phosphate group-introduced product. Also, for substituents
本発明の電気めつき浴添加剤は以下１）〜５）
に示す特徴的作用を有する。
１ めつき皮膜内に分子オーダーでミクロに複合
された有機高分子の作用により塗料との親和
性・結合性（水素結合、キレート結合など）の
増加が得られる。その結果極めて優れた塗料密
着性および２次（耐水）密着性の機能が発現す
る。
２ めつき皮膜内、即ちめつき結晶粒子内および
粒界に共析した有機高分子の絶縁効果あるいは
防錆性により耐蝕性が増加する。
３ また結晶の微細化およびめつき表面の凹凸化
により、有効表面積の増加やアンカー効果が発
現して塗料密着性が向上し、また結晶の微細化
により緻密な膜となつて耐蝕性が向上する。
４ １）と２）の相乗効果により、一層優れた塗
料密着性、耐蝕性に優れためつき皮膜となる。
５ めつき浴に配合する水溶性有機高分子の分子
量、基本骨格、極性基の種類とその密度、配合
濃度および電解条件の相互作用により、めつき
マトリツクス中への水溶性有機高分子の共析量
が決まる。また上記相互作用によりめつき結晶
粒子径およびその形状がコントロールできる
が、特に分子量と極性基の種類とその密度が結
晶粒子径および形状に大きな影響を与える。
〔実施例〕
以下実施例を用いて本発明を更に詳細に説明す
るが、本発明は以下の実施例に限定されるもので
はない。
(1) めつき方法
前処理：冷延鋼板をアルカリ電解脱脂、水洗
後、次の条件でめつきを施した。
めつき浴：用いためつき基本浴の組成を表１
に、ヒドロキシスチレン系重合体およ
び比較例に用いた有機物および有機高
分子の種類を表２に示した。これらを
組み合わせた有機高分子複合めつき浴
の組成を表３に示した。
めつき条件：電流密度４〜200A／ｄm2の直流
電流を用い、浴温30〜600℃の範囲で
めつきを行つた。めつき皮膜厚は全て
3μとした。膜厚測定には過電流式膜
厚計（サンコウ電子(株)、SL−2L−
SM型）を用いた。
尚、多層めつきの製造例（表４）中の溶融めつ
き鋼板の各種は市販のものを使用した。
(2) 塗装方法
塗料として焼付型粉体ポリエステル塗料（日本
ペイント(株)NPC300）を用いた。これをめつき表
面に直接静電噴霧塗装後、230℃、５分間焼付け
て40μの膜厚とした。
尚、比較品の化成処理のリン酸塩処理およびク
ロメート処理にはそれぞれ日本パーカライジング
製ボンデライト3004のリン酸亜鉛処理および日本
ペイント(株)製クロメート処理薬剤（グラノヂン
92）を用いた。
(3) 耐蝕性評価
板橋理化(株)製塩水噴霧試験機を用いてJIS2371
に基づいて５％NaClを２週間連続噴霧を行つた。
表３は本発明品のヒドロキシスチレン系重合体
添加剤を配合しためつき浴から得られた各種めつ
き金属材（単層めつきの場合）の塗膜１次、２次
（耐水）密着性、耐蝕性を比較品とともに示した
ものである。
ゴバン目試験による塗膜１次密着性評価結果に
おいては、比較品No.78、79を除いて本発明品（No.
１〜70）と比較品（No.71〜98）との間に有意差は
認められない。
しかし、エリクセン押出試験による厳しい条件
下での塗膜密着性評価結果においては、顕著な差
が存在していることがわかる。即ち、先ず有機高
分子を全く含まないZn合金めつき皮膜（No.71〜
80）と比較すると、有機高分子を複合した本発明
品（No.１〜70）の塗膜密着性が極めて優れている
ことがわかる。つぎに本発明の条件を満たさない
水溶性有機高分子を含んだめつき浴から得られる
めつき皮膜の場合を、比較品No.81〜90として示
す。これらの浴により得られるめつき皮膜によつ
ても塗料の１次密着力は有機高分子を全く含まな
い亜鉛または亜鉛合金めつきに比べて改善される
場合もあるが、しかし本発明品に比べてみると機
能的に著しく劣つていることがわかる。また、本
発明の条件を満たす有機高分子をめつき浴に含ん
でいても、その配合量が少なく、かつめつき皮膜
中への共析量が少ない複合めつき（No.91、92）で
は塗料密着性の改善が充分に行われないことがわ
かる。次に化成処理を施しためつき鋼板（No.93〜
98）と本発明品とを比較すると、ポリマー共析量
の少ないNo.１の本発明品が比較品と同等である以
外は、全て本発明品が比較品を上回る塗膜１次密
着性を示すことがわかる。
耐水密着性評価結果においては、有機高分子を
含まないNo.71〜80の比較品及びNo.81〜92の比較
品、化成処理鋼板（No.93〜98）の比較品と本発明
品（No.１〜70）とを比較すると、有機高分子の共
析量が比較的少ない本発明品No.１が比較較品No.94
（化成処理板は塗料密着機能のバラツキが大きい）
と同等である以外は本発明品（No.２〜70）が全て
の比較品を上回る性能を示すことが判明した。
以上の結果から、ヒドロキシスチレン系重合体
を少量亜鉛金属と共析させることによつて亜鉛系
めつき表面の塗料の１次および２次密着性が著し
く改良されることがわかつた。
耐蝕性については本発明品No.１が比較品（No.
94，96，98）と同等である以外は本発明品（No.２
〜70）が比較品（No.71〜98）のいずれをも大幅に
上回る結果が得られ、本発明添加剤による複合め
つき皮膜は耐蝕性改善にも顕著な効果があること
がわかる。
表４は本発明の添加剤を配合しためつき浴より
得られた各種多層めつき金属材の塗膜１次、２次
密着性、耐蝕性を比較例とともに示したものであ
る。純亜鉛系めつき皮膜上に化成処理を施したも
のと比較しても上層にヒドロキシスチレン系重合
体を含有しためつきを施すことにより塗料密着
性、耐蝕性ともに大幅に向上していることがわか
る。この結果から、本発明添加剤は下層めつき皮
膜のもつ物性を生かしつつ、その表面層に本発明
の特徴である塗料密着性、耐蝕性などの機能を付
与できることがわかる。
〔発明の効果〕
本発明の添加剤は上記のように、特定の化学構
造を有した水溶性の有機高分子を用いたところに
大きな特徴を有している。本発明の添加剤を用い
た金属浴ではめつき金属と有機高分子との複合化
が分子オーダーであるいは極めてミクロに生じる
ため、比較的少量の有機高分子の共析で高水準の
塗料密着性、耐蝕性等の付与が何能である。従つ
て、従来一般に行われていたリン酸塩処理やクロ
メート処理などの塗装下地処理（化成処理）を全
く施すことなく直接塗装できるので、煩雑でかつ
公害対策の必要な化成処理を省略することが可能
である。この工業的メリツトは多大である。更
に、本発明の添加剤を配合しためつき浴から得ら
れるめつき皮膜はもろい化成処理皮膜を介在しな
い塗装金属材の製造が実現できるので、本発明添
加剤を用いることによつて塗装後のプレス加工に
優れた家電機器用または建材用の理想的なプレコ
ート鋼板の製造が可能である。
本発明の添加剤を用いると、塗料密着性、塗装
後耐蝕性に特に優れ、プレス加工性、溶接性も兼
備しためつき皮膜が生成できるので、自動車用防
錆鋼板に応用すれば、極めて優れた耐蝕性をもつ
た防錆鋼板となりうる。
また、本発明の添加剤を用いためつき皮膜は塗
料のみでなくゴム、有機フイルム、セラミツクス
などのラミネート下地表面としても利用できる。
更に、本発明の添加剤は食罐などの罐用材料、
銅箔などの電子材料、装飾品などの製造の際のめ
つき浴添加剤として用いることができる。
また、本発明の添加剤はめつきスケールアツプ
にも容易に対応でき、しかも従来の電気めつき設
備で容易に使用でき、高価な設備や多大の労力を
必要とせず、工業的価値が高い。
更に、本発明の添加剤は、全ての電気めつきに
有効であるが、特に亜鉛または亜鉛合金めつき浴
に用いた場合には一層有効であり、かつ被めつき
金属材が鉄鋼板である場合に、本発明の効果を最
大に引き出すことができる。
更に本発明の添加剤は、Al2O3、SiO2などのセ
ラミツクス粒子あるいは水不溶性高分子を複合す
る分散めつきにも用いることができ、本添加剤の
配合により、高度な塗料密着性や、塗装後耐蝕性
の機能を有した分散めつき皮膜の製造が可能であ
る。従来の分散めつき皮膜は特に塗料の耐水密着
性に欠点を有しているので、本添加剤配合は極め
て有力な改善技術となる。
The electroplating bath additives of the present invention are as follows 1) to 5)
It has the characteristic effects shown below. 1. Increased affinity and bonding properties (hydrogen bonds, chelate bonds, etc.) with paints can be obtained due to the action of organic polymers that are micro-compounded on a molecular order within the plating film. As a result, extremely excellent paint adhesion and secondary (water resistant) adhesion functions are achieved. 2. Corrosion resistance is increased due to the insulating effect or antirust property of the organic polymer eutectoided within the plating film, that is, within the plating crystal grains and at the grain boundaries. 3 In addition, the finer crystals and unevenness of the plated surface increase the effective surface area and create an anchor effect, improving paint adhesion, and the finer crystals form a dense film, improving corrosion resistance. . 4 The synergistic effect of 1) and 2) results in a fading film with even better paint adhesion and corrosion resistance. 5 Co-deposition of the water-soluble organic polymer into the plating matrix due to the interaction of the molecular weight, basic skeleton, type of polar group and density of the water-soluble organic polymer blended in the plating bath, blending concentration, and electrolytic conditions. The amount is determined. Furthermore, the diameter and shape of the plated crystal particles can be controlled by the above-mentioned interaction, but the molecular weight, type of polar group, and density thereof have a particularly large influence on the diameter and shape of the crystal particles. [Examples] The present invention will be explained in more detail using Examples below, but the present invention is not limited to the Examples below. (1) Plating method Pretreatment: Cold rolled steel sheets were subjected to alkaline electrolytic degreasing and washing with water, and then plated under the following conditions. Plating bath: Table 1 shows the composition of the basic plating bath used.
Table 2 shows the types of organic substances and organic polymers used in the hydroxystyrene polymer and comparative examples. Table 3 shows the composition of an organic polymer composite plating bath that combines these. Plating conditions: Plating was carried out using a direct current with a current density of 4 to 200 A/dm 2 and at a bath temperature of 30 to 600°C. All plating film thicknesses are
It was set to 3μ. For film thickness measurement, use an overcurrent film thickness meter (Sanko Denshi Co., Ltd., SL-2L-
SM type) was used. In addition, various types of hot-dip galvanized steel plates in the multilayer plating production examples (Table 4) were commercially available. (2) Painting method Baking type powder polyester paint (NPC300, Nippon Paint Co., Ltd.) was used as the paint. This was electrostatically sprayed directly onto the plating surface and baked at 230°C for 5 minutes to give a film thickness of 40μ. In addition, the phosphate treatment and chromate treatment of the chemical conversion treatment of comparative products were respectively zinc phosphate treatment of Bonderite 3004 manufactured by Nippon Parkerizing Co., Ltd. and chromate treatment agent (Granodin) manufactured by Nippon Paint Co., Ltd.
92) was used. (3) Corrosion resistance evaluation JIS2371 using a salt spray tester manufactured by Itabashi Rika Co., Ltd.
Based on this, 5% NaCl was continuously sprayed for two weeks. Table 3 shows the primary and secondary (water resistant) adhesion of various plated metal materials (in the case of single layer plating) obtained from the matting bath containing the hydroxystyrene polymer additive of the present invention. Corrosion resistance is shown together with comparative products. In the results of the primary adhesion evaluation of the paint film by the goblin test, the present invention product (No.
No. 1 to 70) and the comparative products (No. 71 to 98), no significant difference was observed. However, it can be seen that there are significant differences in the results of coating film adhesion evaluation under severe conditions using the Erichsen extrusion test. That is, first, a Zn alloy plating film (No. 71 ~
80), it can be seen that the products of the present invention (Nos. 1 to 70), which are composites of organic polymers, have extremely excellent coating film adhesion. Next, cases of plating films obtained from plating baths containing water-soluble organic polymers that do not satisfy the conditions of the present invention are shown as comparative products No. 81 to 90. Although the primary adhesion of the coating film obtained by these baths may be improved compared to zinc or zinc alloy plating that does not contain any organic polymer, however, compared to the product of the present invention, As you can see, it is significantly inferior in terms of functionality. Furthermore, even if the plating bath contains an organic polymer that satisfies the conditions of the present invention, the compounded amount is small and the amount eutectoided into the plating film is small in composite plating (No. 91, 92). It can be seen that the paint adhesion was not sufficiently improved. Next, we applied a chemical conversion treatment to a matted steel plate (No. 93~
98) and the products of the present invention, all of the products of the present invention have better primary adhesion of the coating film than the comparative products, except for the No. 1 inventive product with a small amount of polymer eutectoid, which is equivalent to the comparative product. I understand what is shown. In the water resistant adhesion evaluation results, comparison products No. 71 to 80 and comparison products No. 81 to 92 that do not contain organic polymers, comparison products of chemically treated steel sheets (No. 93 to 98), and the invention product ( Comparing Nos. 1 to 70), the present invention product No. 1, which has a relatively small eutectoid amount of organic polymer, is the comparative product No. 94.
(Chemical conversion treated boards have large variations in paint adhesion ability.)
It was found that the products of the present invention (Nos. 2 to 70) exhibited better performance than all comparative products, except that they were equivalent to the following. From the above results, it was found that by eutectoiding a small amount of hydroxystyrene polymer with zinc metal, the primary and secondary adhesion of the paint to the zinc-plated surface was significantly improved. Regarding corrosion resistance, the invention product No. 1 is superior to the comparative product (No. 1).
The product of the present invention (No. 2) except that it is equivalent to 94, 96, 98)
-70) were significantly superior to all of the comparative products (Nos. 71 to 98), indicating that the composite plating film using the additive of the present invention has a remarkable effect on improving corrosion resistance. Table 4 shows the primary and secondary coating film adhesion and corrosion resistance of various multilayer plated metal materials obtained from the tanning bath containing the additives of the present invention, together with comparative examples. Even compared to a pure zinc plating film that has undergone chemical conversion treatment, applying a plating film containing a hydroxystyrene polymer to the upper layer significantly improves both paint adhesion and corrosion resistance. Recognize. These results show that the additive of the present invention can provide the surface layer with functions such as paint adhesion and corrosion resistance, which are the characteristics of the present invention, while taking advantage of the physical properties of the lower plating film. [Effects of the Invention] As described above, the additive of the present invention has a major feature in that it uses a water-soluble organic polymer having a specific chemical structure. In the metal bath using the additive of the present invention, the plating metal and the organic polymer are composited on the molecular order or extremely microscopically, so a high level of paint adhesion can be achieved with a relatively small amount of eutectoid of the organic polymer. , has the ability to impart corrosion resistance, etc. Therefore, it is possible to directly apply the paint without any pre-painting treatment (chemical conversion treatment) such as phosphate treatment or chromate treatment, which was conventionally generally performed, so it is possible to omit the complicated chemical conversion treatment that requires anti-pollution measures. It is possible. The industrial benefits are enormous. Furthermore, the plating film obtained from the tanning bath containing the additive of the present invention enables the production of coated metal materials without intervening brittle chemical conversion treatment films. It is possible to manufacture ideal pre-painted steel sheets for home appliances or building materials that have excellent press processing properties. When the additive of the present invention is used, it is possible to form a tacky film with particularly excellent paint adhesion and post-painting corrosion resistance, as well as press workability and weldability. It can be used as a rust-proof steel plate with excellent corrosion resistance. In addition, the stain film using the additive of the present invention can be used not only as a paint but also as a base surface for laminates such as rubber, organic film, and ceramics. Furthermore, the additive of the present invention can be used as a material for cans such as food cans,
It can be used as a plating bath additive in the production of electronic materials such as copper foil, decorative items, etc. Further, the additive of the present invention can easily cope with plating scale-up, can be easily used in conventional electroplating equipment, does not require expensive equipment or a great deal of labor, and has high industrial value. Furthermore, although the additive of the present invention is effective for all types of electroplating, it is particularly effective when used in zinc or zinc alloy plating baths, and when the metal material to be plated is a steel plate. In this case, the effects of the present invention can be maximized. Furthermore, the additive of the present invention can also be used for dispersion plating in which ceramic particles such as Al 2 O 3 and SiO 2 or water-insoluble polymers are composited. , it is possible to produce a dispersion-plated film that has a corrosion-resistant function after painting. Since conventional dispersion plating films have drawbacks, particularly in the water-resistant adhesion of paints, this additive formulation is an extremely effective improvement technique.
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】
注１ 金属中炭素分析装置（堀場製作所製EMIA
−110）を用いて1350℃に加熱し、発生する
CO2，CO量を検出してめつき皮膜中の全炭
素量を定量（wt％）した。この値（炭素含
量）をもつて有機高分子の共析量とした。
注２ 下地めつき面に達するゴバン目を１mm間隔
に100個描き、セロテープで剥離した時の塗
膜残存数で示した。
注３ 下地めつき面に達するゴバン目を１mm間隔
で100個描いた後エリクセン押出工を行い、
引き続きセロテープ剥離試験を行つた際の塗
膜残存率で示した。
評価基準
Ａ…… ９mmの押出加工後のテープ剥離による剥
離が全く認められない。
Ｂ…… ８mmの押出加工後のテープ剥離による剥
離が全く認められない。
Ｃ…… ７mmの押出加工後のテープ剥離による剥
離が全く認められない。
Ｄ…… ６mmの押出加工後のテープ剥離による剥
離が100/100未満である。
注４） ゴバン目を描かない状態で60℃のイオン
交換水に連続浸漬し、注２）のゴバン目試験を
行つた際の塗膜残存率で示した。評価結果は
Ａ…… 180日間の浸漬でも剥離が認められな
い（100/100）。
Ｂ…… 150日間の浸漬でも剥離が認められな
い（100/100）
Ｃ…… 120日間の浸漬でも剥離が認められな
い（100/100）
Ｄ…… 100日間の浸漬でも剥離が認められな
い（100/100）。
Ｅ……100日未満の浸漬で剥離が認められる。
注５） 塗装後クロスカツトを入れた調整片を
JIS2371に基づいて５％塩化ナトリウム水溶液
連続噴霧を行つた後、クロスカツト部のテープ
剥離試験を行い、カツトラインからの塗膜剥離
幅（片幅）で示す。
評価基準
Ａ…… ３週間の連続噴霧後で、１mm以内の剥
離幅、クロスカツト周辺部に塗膜ふくれな
し。
Ｂ…… ２週間連続噴霧後で、１mm以内の剥離
幅、周辺部にふくれなし。
Ｃ…… １週間の連続噴霧後で、１mm以内の剥
離幅、周辺部にふくれなし。
Ｄ…… １週間の連続噴霧後で、１mmを超える
剥離が認められる。
Ｅ…… １週間の連続噴霧後で、１mmを超える
剥離が認められ、周辺部にふくれも認められ
る。[Table] Note 1 Metal carbon analyzer (Horiba, Ltd. EMIA
−110) and heated to 1350°C to generate
The amount of CO 2 and CO was detected and the total amount of carbon in the plating film was determined (wt%). This value (carbon content) was taken as the eutectoid amount of the organic polymer. Note 2: 100 goblets reaching the base plated surface were drawn at 1 mm intervals, and the number of coatings remaining when removed with cellophane tape was indicated. Note 3 After drawing 100 gobbins at 1mm intervals that reach the base plating surface, perform Erichsen extrusion.
It was expressed as the coating film remaining rate when a cellophane tape peeling test was subsequently performed. Evaluation Criteria A: No peeling due to tape peeling after extrusion processing of 9 mm was observed. B...No peeling due to tape peeling after 8 mm extrusion processing was observed. C... No peeling due to tape peeling after 7 mm extrusion processing was observed. D... Peeling by tape peeling after 6 mm extrusion processing is less than 100/100. Note 4) It is expressed as the coating film survival rate when the test of note 2) was conducted by continuously immersing the product in ion-exchanged water at 60°C without any markings. The evaluation result was A... No peeling was observed even after 180 days of immersion (100/100). B... No peeling observed even after 150 days of immersion (100/100) C... No peeling observed even after 120 days of immersion (100/100) D... No peeling observed even after 100 days of immersion (100/100) 100/100). E: Peeling is observed after immersion for less than 100 days. Note 5) After painting, remove the adjustment piece with the cross cut.
After continuously spraying a 5% sodium chloride aqueous solution in accordance with JIS2371, a tape peeling test was performed on the cross-cut area, and the peeling width (single width) from the cut line is shown. Evaluation Criteria A: After 3 weeks of continuous spraying, peeling width within 1 mm, no blistering of the coating around the cross cut. B... After continuous spraying for 2 weeks, peeling width within 1 mm, no blistering around the periphery. C... After continuous spraying for one week, peeling width within 1 mm, no blisters around the periphery. D... After continuous spraying for one week, peeling of more than 1 mm is observed. E... After one week of continuous spraying, peeling of more than 1 mm was observed, and blisters were also observed in the surrounding area.
Claims (1)
スチレン系重合体またはこれらの誘導体からなる
水溶性の有機高分子の１種以上を主成分として含
むことを特徴とする電気めつき浴添加剤。 ２ 水溶性有機高分子が次の一般式(A) （式中；ｍ，ｎはｍ≧０、ｎ≧３でそれぞれ一
般式(A)の有機高分子の重量平均分子量が100万に
なるまでの任意の数、 ；０≦ｋ≦２， ；０≦ｐ≦２， ；ただしｋ＋ｐ＋ｍ＞０， ；R1〜R3はＨまたは炭素数１〜５のアルキル
基、 ；Ｘは重合性のビニル系単量体、 ；Ｙ，Ｚは同種または異種であり、かつ −SO3M，−CH2−SO3M，−Y1，−OCH3， 【式】【式】 【式】【式】 【式】−（CH2）tY4， −CH2OH から選ばれるものであつて、〔式中 ；ＭはＨ、アルカリ金属、アルカリ土類金属、
またはアミン類などの有機カチオン、 ；Y1，Y4はハロゲン ；Y2-〜Y3-はハロゲイオン、有機酸アニオン、
無機酸アニオンなどの対イオン ；ＷはＳまたは０ ；R4〜R6は同種または異種であつて、直鎖ま
たは分岐鎖アルキル基あるいはヒドロキシア
ルキル基等のアルキル基誘導体または芳香族
基、またはR4とR5はＮ基とで環を形成して
いてもかまわない。さらにR6はＨをとり得
る。 ；R7〜R13は同種または異種であつて、直鎖ま
たは分岐鎖アルキル基、あるいはヒドロキシ
アルキル基等のアルキル誘導体基、芳香族
基、またはＨ ；ｑ，ｓ，ｔ，ｕは０または１ ；ｒは０，１または２を示す〕） で表されるアニオン性、カチオン性または両性の
ヒドロキシスチレン系の水溶性有機高分子である
特許請求の範囲第１項記載の添加剤。 ３ 水溶性有機高分子が一般式(A)の置換基の水酸
基（−OH）をパラ位に有するものである特許請
求の範囲第２項記載の添加剤。 ４ 水溶性有機高分子が一般式(A)に於いてｍ＝
０、置換基の水酸基（−OH）がパラ位である、
即ち次の一般式(B) （式中、R1〜R3、Ｙ，Ｚ，ｋ，ｐ，ｎは前記
に同じ）で表される有機高分子である特許請求の
範囲第２項または第３項記載の添加剤。 ５ 水溶性有機高分子の構造が（Ｙ）k＝（SO3M）
k，（Ｍは前記に同じ、０＜ｋ≦２）である特許請
求の範囲第２項〜第４項の何れか１項に記載の添
加剤。 ６ 水溶性有機高分子の構造が（Ｚ）p＝（Br）p
（０≦ｐ≦２）である特許請求の範囲第２項〜第
５項の何れか１項に記載の添加剤。 ７ 水溶性有機高分子の構造が（Ｚ）p＝ 【式】（０＜ｐ≦２）である特 許請求の範囲第２項〜第５項の何れか１項に記載
の添加剤。 ８ 水溶性有機高分子の構造が（Ｚ）p＝ 【式】（０＜ｐ≦２） である特許請求の範囲第２項〜第５項の何れか１
項に記載の添加剤。 ９ 水溶性有機高分子の構造が（Ｚ）p＝ 【式】（０＜ｐ≦２） である特許請求の範囲第２項〜第５項の何れか１
項に記載の添加剤。 １０ 水溶性有機高分子の構造がｋ＝０である特
許請求の範囲第６項〜第９項の何れか１項に記載
の添加剤。 １１ 水溶性有機高分子の構造がR1＝R2＝R3＝
Ｈである特許請求の範囲第４項〜第１０項の何れ
か１項に記載の添加剤。[Scope of Claims] 1. Electroplating characterized by containing as a main component one or more water-soluble organic polymers made of hydroxystyrene polymers or derivatives thereof having a weight average molecular weight of 10 million to 1 million. Bath additive. 2 The water-soluble organic polymer has the following general formula (A) (In the formula; m and n are arbitrary numbers until m≧0 and n≧3, respectively, and the weight average molecular weight of the organic polymer of general formula (A) is 1 million, ;0≦k≦2, ;0 ≦p≦2, ; However, k+p+m>0, ; R 1 to R 3 are H or an alkyl group having 1 to 5 carbon atoms, ; X is a polymerizable vinyl monomer, ; Y and Z are the same or different types; Yes, and −SO 3 M, −CH 2 −SO 3 M, −Y 1 , −OCH 3 , [Formula] [Formula] [Formula] [Formula] [Formula] −(CH 2 )tY 4 , −CH 2 OH, [wherein M is H, alkali metal, alkaline earth metal,
or organic cations such as amines; Y 1 and Y 4 are halogens; Y 2- to Y 3- are halogen ions, organic acid anions,
Counter ion such as an inorganic acid anion; W is S or 0; R 4 to R 6 are the same or different, and are an alkyl group derivative such as a straight or branched alkyl group or a hydroxyalkyl group, or an aromatic group, or R 4 and R 5 may form a ring with the N group. Furthermore, R 6 can be H. ; R 7 to R 13 are the same or different and are linear or branched alkyl groups, alkyl derivative groups such as hydroxyalkyl groups, aromatic groups, or H; q, s, t, and u are 0 or 1; ; r represents 0, 1 or 2]) The additive according to claim 1, which is an anionic, cationic or amphoteric hydroxystyrene water-soluble organic polymer. 3. The additive according to claim 2, wherein the water-soluble organic polymer has a hydroxyl group (-OH) of the substituent of general formula (A) at the para position. 4 The water-soluble organic polymer in general formula (A) has m=
0, the hydroxyl group (-OH) of the substituent is in the para position,
That is, the following general formula (B) The additive according to claim 2 or 3 , which is an organic polymer represented by the formula (wherein R1 to R3, Y, Z, k, p, and n are the same as above). 5 The structure of a water-soluble organic polymer is (Y) k = (SO 3 M)
The additive according to any one of claims 2 to 4, wherein k , (M is the same as above, 0<k≦2). 6 The structure of a water-soluble organic polymer is (Z) p = (Br) p
The additive according to any one of claims 2 to 5, wherein (0≦p≦2). 7. The additive according to any one of claims 2 to 5, wherein the water-soluble organic polymer has a structure (Z) p = [formula] (0<p≦2). 8 Any one of claims 2 to 5, wherein the water-soluble organic polymer has the structure (Z) p = [Formula] (0<p≦2)
Additives listed in section. 9 Any one of claims 2 to 5, wherein the structure of the water-soluble organic polymer is (Z) p = [Formula] (0<p≦2)
Additives listed in section. 10. The additive according to any one of claims 6 to 9, wherein the water-soluble organic polymer has a structure of k=0. 11 The structure of water-soluble organic polymer is R 1 = R 2 = R 3 =
The additive according to any one of claims 4 to 10, which is H.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27352386A JPS63128193A (en) | 1986-11-17 | 1986-11-17 | Additive for electroplating bath |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27352386A JPS63128193A (en) | 1986-11-17 | 1986-11-17 | Additive for electroplating bath |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63128193A JPS63128193A (en) | 1988-05-31 |
| JPH0319319B2 true JPH0319319B2 (en) | 1991-03-14 |
Family
ID=17529039
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27352386A Granted JPS63128193A (en) | 1986-11-17 | 1986-11-17 | Additive for electroplating bath |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63128193A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01290797A (en) * | 1988-05-17 | 1989-11-22 | Nippon Steel Corp | Composite electroplated steel sheet having superior corrosion resistance |
| JPH01309998A (en) * | 1988-06-07 | 1989-12-14 | Nippon Steel Corp | Production of composite electroplated steel sheet having superior corrosion resistance and fine surface luster |
| KR100506393B1 (en) * | 2000-12-13 | 2005-08-10 | 주식회사 포스코 | method of producing solution for electrodeposition |
-
1986
- 1986-11-17 JP JP27352386A patent/JPS63128193A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63128193A (en) | 1988-05-31 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |