JP2018521225A - Surface treatment agent for galvanized steel sheet with low environmental impact, galvanized steel sheet, and method for producing galvanized steel sheet - Google Patents
Surface treatment agent for galvanized steel sheet with low environmental impact, galvanized steel sheet, and method for producing galvanized steel sheet Download PDFInfo
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- JP2018521225A JP2018521225A JP2018502396A JP2018502396A JP2018521225A JP 2018521225 A JP2018521225 A JP 2018521225A JP 2018502396 A JP2018502396 A JP 2018502396A JP 2018502396 A JP2018502396 A JP 2018502396A JP 2018521225 A JP2018521225 A JP 2018521225A
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- steel sheet
- galvanized steel
- parts
- surface treatment
- treatment agent
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Links
- 229910001335 Galvanized steel Inorganic materials 0.000 title claims abstract description 100
- 239000008397 galvanized steel Substances 0.000 title claims abstract description 100
- 230000007613 environmental effect Effects 0.000 title claims abstract description 45
- 239000012756 surface treatment agent Substances 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 60
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 24
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 24
- 239000004952 Polyamide Substances 0.000 claims abstract description 23
- 229920002647 polyamide Polymers 0.000 claims abstract description 23
- 125000002091 cationic group Chemical group 0.000 claims abstract description 21
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 21
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 20
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 17
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 14
- 239000011574 phosphorus Substances 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 13
- 239000004593 Epoxy Substances 0.000 claims abstract description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 239000011737 fluorine Substances 0.000 claims abstract description 7
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 7
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 6
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 claims abstract description 5
- 125000000524 functional group Chemical group 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims description 45
- 239000011248 coating agent Substances 0.000 claims description 42
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- 239000002131 composite material Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- -1 hydroxysiloxane Chemical class 0.000 claims description 10
- 238000004381 surface treatment Methods 0.000 claims description 10
- 229910052720 vanadium Inorganic materials 0.000 claims description 10
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 10
- 150000002894 organic compounds Chemical class 0.000 claims description 8
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 claims description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 239000007822 coupling agent Substances 0.000 abstract description 6
- 150000001282 organosilanes Chemical class 0.000 abstract description 6
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 abstract 1
- 239000010408 film Substances 0.000 description 73
- 229910000831 Steel Inorganic materials 0.000 description 39
- 239000010959 steel Substances 0.000 description 39
- 238000005260 corrosion Methods 0.000 description 38
- 230000007797 corrosion Effects 0.000 description 38
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 17
- 238000012360 testing method Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 239000010410 layer Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 9
- 239000003973 paint Substances 0.000 description 9
- 239000003513 alkali Substances 0.000 description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 7
- 229910052804 chromium Inorganic materials 0.000 description 7
- 239000011651 chromium Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000007921 spray Substances 0.000 description 7
- 239000013527 degreasing agent Substances 0.000 description 6
- 238000005237 degreasing agent Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000000314 lubricant Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229920005830 Polyurethane Foam Polymers 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000001050 lubricating effect Effects 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 5
- 229920002635 polyurethane Polymers 0.000 description 5
- 239000004814 polyurethane Substances 0.000 description 5
- 239000011496 polyurethane foam Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229920000180 alkyd Polymers 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 150000000703 Cerium Chemical class 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 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 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002816 nickel compounds Chemical class 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- NFVUDQKTAWONMJ-UHFFFAOYSA-I pentafluorovanadium Chemical compound [F-].[F-].[F-].[F-].[F-].[V+5] NFVUDQKTAWONMJ-UHFFFAOYSA-I 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 description 2
- 150000003755 zirconium compounds Chemical class 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- FZIZEIAMIREUTN-UHFFFAOYSA-N azane;cerium(3+) Chemical compound N.[Ce+3] FZIZEIAMIREUTN-UHFFFAOYSA-N 0.000 description 1
- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical compound [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material 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
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 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
- 230000035515 penetration Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229940098458 powder spray Drugs 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002937 thermal insulation foam Substances 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
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Laminated Bodies (AREA)
Abstract
【課題】環境負荷の小さい亜鉛めっき鋼板用表面処理剤、亜鉛めっき鋼板及び亜鉛めっき鋼板の製造方法の提供。
【解決手段】環境負荷の小さい亜鉛めっき鋼板用表面処理剤。その水溶液は以下の質量部の固体成分：封鎖型変性カチオン性ポリウレタン樹脂Ａ３０〜５５部；少なくとも１個の活性水素アミノ官能基を含む有機シランカップリング剤Ｂ１と、少なくとも１個のエポキシ官能基を含む有機シランカップリング剤Ｂ２とを含み、Ｂ１／Ｂ２が０．４〜１であるシランカップリング剤Ｂ３２〜６０部；表面グラフト化高密度ポリエチレン粒子又は表面グラフト化ポリアミド粒子Ｃ３〜１５部；バナジウム元素換算でバナジウム含有化合物Ｄ０．０１〜０．５部；リン元素換算でリン含有化合物Ｅ０．５〜１．５部；チタン元素換算でフッ素含有チタン化合物Ｆ０．１〜１部；及びセリウム元素換算でセリウム含有化合物Ｇ０．０１〜１部を含む。
【選択図】なしA surface treatment agent for a galvanized steel sheet having a low environmental load, a galvanized steel sheet, and a method for producing the galvanized steel sheet.
A surface treatment agent for a galvanized steel sheet having a small environmental load. The aqueous solution contains the following solid components of 30 parts by mass: blocked modified cationic polyurethane resin A-55 parts; organosilane coupling agent B1 containing at least one active hydrogen amino functional group, and at least one epoxy functional group. An organic silane coupling agent B2 and a silane coupling agent B32-60 parts having a B1 / B2 of 0.4-1; surface grafted high density polyethylene particles or surface grafted polyamide particles C3-15 parts; vanadium Vanadium-containing compound D 0.01-0.5 part in terms of element; Phosphorus-containing compound E 0.5-1.5 parts in terms of phosphorus element; Fluorine-containing titanium compound F0.1-1 parts in terms of titanium element; and cerium element equivalent And 0.01 to 1 part of cerium-containing compound G.
[Selection figure] None
Description
本発明は表面処理剤に関し、具体的には鋼板を被覆する表面処理剤に関する。本発明はまた、上記表面処理剤で被覆した鋼板及び上記鋼板の製造方法に関する。 The present invention relates to a surface treatment agent, and specifically to a surface treatment agent for coating a steel sheet. The present invention also relates to a steel sheet coated with the surface treatment agent and a method for producing the steel sheet.
亜鉛めっき鋼板は、一般的に自動車、家庭用機器、ＯＡ製品などの部品として用いられる。特に車の車体及び他の部品に用いられる場合、亜鉛めっき鋼板は、深絞り加工などのスタンプ成形工程が施される。輸送時及び保管時に亜鉛めっき鋼板が腐食して白錆が発生するのを防止するために、製造時に鋼板を錆止め油で被覆する必要がある。また、部品のスタンプ成形中の金型と鋼板との摩擦を低減して亜鉛層の亀裂及び表面摩耗を防ぐために、スタンプ成形工程では金型に潤滑油を加えなければならず、部品の成形後に脱脂洗浄を行う。同時に、外部部品としての耐腐食性要件を満たすように、亜鉛めっき鋼板を塗装（粉末スプレー又はスプレーコーティング）しなければならない。冷蔵庫、冷凍庫及び商業用空調産業では亜鉛めっき鋼板と発泡接着材（通常はポリウレタン又はポリスチレン）との良好な密着性が要求される。したがって、亜鉛めっき鋼板は塗装性についても高い要件が求められる。保管及び輸送時に錆止め油、潤滑油及び脱脂剤を用いると、環境に負担をかけ、製造コストも上昇する。亜鉛めっき鋼板の耐腐食性及び加工成形性を向上させるために、従来技術では、亜鉛めっき鋼板の耐腐食性を向上させるために亜鉛めっき鋼板をクロム酸塩不動態化処理する方法が採用されている。しかしながら、この方法では亜鉛めっき鋼板の加工成形性の改善の程度が限られる。現在、亜鉛めっき鋼板の耐腐食性と潤滑効果とのバランスが取れるように、クロム酸塩不動態化処理に加えて有機樹脂の固体潤滑膜（通常は、低表面エネルギーポリマー、例えばポリオレフィン及びポリテトラフルオロエチレンなど）を被覆する別の方法もある。しかしながら、固体潤滑膜を追加すると鋼板の表面エネルギーが減少して、後で被膜する膜に対する鋼板の密着性が大幅に低下し、鋼板の塗装性に影響を及ぼす。環境に関する指令が絶え間なく公布されるのに伴って、クロムめっきした亜鉛めっき鋼板は、クロムを含まない環境負荷の小さい製品に徐々に取って代わられている。 Galvanized steel sheets are generally used as parts for automobiles, household equipment, OA products and the like. In particular, when used in a car body and other parts of a car, the galvanized steel sheet is subjected to a stamp forming process such as deep drawing. In order to prevent the galvanized steel sheet from corroding and generating white rust during transportation and storage, it is necessary to coat the steel sheet with anti-rust oil during production. Also, in order to reduce the friction between the mold and the steel plate during stamping of the part and prevent cracking and surface wear of the zinc layer, lubricant must be added to the mold in the stamping process. Perform degreasing cleaning. At the same time, the galvanized steel sheet must be painted (powder spray or spray coating) to meet the corrosion resistance requirements as external parts. In the refrigerator, freezer, and commercial air conditioning industries, good adhesion between a galvanized steel sheet and a foamed adhesive (usually polyurethane or polystyrene) is required. Therefore, galvanized steel sheets are required to have high requirements for paintability. Use of rust-preventing oil, lubricating oil, and degreasing agent during storage and transportation places a burden on the environment and increases manufacturing costs. In order to improve the corrosion resistance and workability of the galvanized steel sheet, the conventional technique employs a chromate passivation treatment method for the galvanized steel sheet to improve the corrosion resistance of the galvanized steel sheet. Yes. However, this method limits the degree of improvement in workability of the galvanized steel sheet. At present, in addition to chromate passivation treatment, organic resin solid lubricating films (usually low surface energy polymers such as polyolefins and polytetra There are other methods of coating such as fluoroethylene. However, when a solid lubricating film is added, the surface energy of the steel sheet is reduced, the adhesion of the steel sheet to the film to be coated later is greatly reduced, and the paintability of the steel sheet is affected. With the continuous promulgation of environmental directives, chrome-plated galvanized steel sheets are gradually being replaced by products with low environmental impact that do not contain chromium.
表面処理の点から、クロムを含まない環境負荷の小さい製品は、無機製品と有機／無機複合製品とに分類できる。無機潤滑膜は、主に、ケイ素、マンガン及びリンなどの無機化合物を含む薄膜である。このような製品は、深絞り加工後の外観及び塗装性が良好である。しかしながら、亜鉛めっき鋼板の耐腐食性は、無機潤滑膜によって大幅に向上させることができない。有機／無機複合潤滑膜は、樹脂、腐食防止剤、シランカップリング剤、シリカコロイド及び固体潤滑剤からなる薄膜である。この膜は、潤滑性、耐腐食性に優れるだけでなく、耐指紋性及び耐アルカリ性も良好である。 From the viewpoint of surface treatment, products that do not contain chromium and have a low environmental impact can be classified into inorganic products and organic / inorganic composite products. The inorganic lubricating film is a thin film mainly containing an inorganic compound such as silicon, manganese and phosphorus. Such products have good appearance and paintability after deep drawing. However, the corrosion resistance of the galvanized steel sheet cannot be significantly improved by the inorganic lubricating film. The organic / inorganic composite lubricant film is a thin film made of a resin, a corrosion inhibitor, a silane coupling agent, a silica colloid, and a solid lubricant. This film not only has excellent lubricity and corrosion resistance, but also has good fingerprint resistance and alkali resistance.
特許文献１（公開日２００９年３月２５日、名称「被覆鋼板及びその製造方法、加工品及び薄型テレビ用パネル」）には、化学膜で被覆された鋼板及び該鋼板の両面に形成された亜鉛系めっき層；上記鋼板の両面に形成された亜鉛系めっき層上に形成されたクロムを含まない化成皮膜；並びに、上記鋼板の片面の上記化成皮膜上に設けられた単層被膜であって、架橋剤で硬化させたポリエステル系樹脂と、平均粒径が３〜４０μｍ、ガラス転移温度が７０〜２００℃で上記ポリエステル系樹脂よりも高い硬度を有する樹脂粒子とを含む単層被膜が開示されている。しかしながら、この特許で開示された技術的解決法は、まず鋼板の表面にクロムを含まない化成皮膜を形成し、その後、ポリエステル樹脂で被覆するという２工程の方法である。すなわち、上記化成皮膜は、被覆を２回、焼き付けを２回行わなければならない複雑な処理工程によって形成されるため、製造設備に対する要求が比較的高い。 In Patent Document 1 (published on March 25, 2009, the name “coated steel sheet and method for manufacturing the same, processed product, and panel for thin television”), the steel sheet coated with a chemical film and formed on both surfaces of the steel sheet. A zinc-based plating layer; a conversion film not containing chromium formed on the zinc-based plating layer formed on both surfaces of the steel sheet; and a single-layer film provided on the conversion film on one side of the steel sheet, , A monolayer coating comprising a polyester resin cured with a crosslinking agent, and resin particles having an average particle diameter of 3 to 40 μm, a glass transition temperature of 70 to 200 ° C. and a hardness higher than that of the polyester resin. ing. However, the technical solution disclosed in this patent is a two-step method in which a chemical conversion film not containing chromium is first formed on the surface of a steel plate and then coated with a polyester resin. That is, since the chemical conversion film is formed by a complicated processing step in which coating is performed twice and baking is performed twice, the demand for manufacturing equipment is relatively high.
特許文献２（公開日２００９年９月１６日、名称「扁平部の耐腐食性及び耐黒変性、スタンプ成形後の外観及び耐腐食性に優れた表面処理亜鉛めっき鋼板及び亜鉛めっき鋼板用水性表面処理液」）には、水性表面処理液が開示されている。上記表面処理液は、特定の比率で水溶性ジルコニウム化合物、水分散性シリカ粒子、シランカップリング剤、バナジン酸化合物、リン酸化合物、ニッケル化合物及びアクリル樹脂乳液を含む。上記表面処理液を被覆して得た表面処理済み亜鉛めっき鋼板は、特定の比率でジルコニウム化合物、シリカ粒子、シランカップリング剤由来成分、バナジン酸化合物、リン酸化合物、ニッケル化合物及びアクリル樹脂を含む表面処理膜を有し、該表面処理膜のＺｒ堆積量は１０〜２００ｍｇ／ｍ２である。しかしながら、上記特許文献に関する技術的解決法においては、アルカリ性脱脂剤での洗浄後の鋼板の塗装性及び耐腐食性について言及されていない。 Patent Document 2 (Publication Date: September 16, 2009, Name “Surface-resistant galvanized steel sheet excellent in corrosion resistance and blackening resistance of flat part, appearance after stamping and corrosion resistance, and aqueous surface for galvanized steel sheet” The treatment liquid ") discloses an aqueous surface treatment liquid. The surface treatment liquid contains a water-soluble zirconium compound, water-dispersible silica particles, a silane coupling agent, a vanadic acid compound, a phosphoric acid compound, a nickel compound, and an acrylic resin emulsion in a specific ratio. The surface-treated galvanized steel sheet obtained by coating the surface treatment liquid contains a zirconium compound, silica particles, a silane coupling agent-derived component, a vanadate compound, a phosphate compound, a nickel compound, and an acrylic resin at a specific ratio. A surface treatment film is provided, and the Zr deposition amount of the surface treatment film is 10 to 200 mg / m 2 . However, the technical solutions relating to the above-mentioned patent documents do not mention the paintability and corrosion resistance of the steel sheet after washing with an alkaline degreasing agent.
特許文献３（公開日２０１０年７月２８日、名称「優れた加工性、耐アルカリ性及び耐溶剤性を有する亜鉛めっき鋼板及び表面処理剤」）は、表面が有機複合保護膜で被覆された亜鉛めっき鋼板に関する。上記亜鉛めっき鋼板は、Ａ）伸びが２０〜１００％、ガラス転移温度が５０〜１００℃のカチオン性ポリウレタン樹脂を５０〜７０重量％；Ｂ）粒径（メジアン径）が１〜２μｍの酸化ポリエチレン粒子を５〜１０％；Ｃ）少なくとも１個の活性水素を含む１個以上のアミノ官能基を含む１種以上のオルガノシランカップリング剤（Ｃａ）及び少なくとも１個のエポキシ官能基を含む１種以上のオルガノシランカップリング剤（Ｃｂ）を重量比（Ｃａ）／（Ｃｂ）０．２〜０．４、カチオン性ポリウレタン樹脂（Ａ）の総量とオルガノシランカップリング剤の総量との重量比（Ａ）／（Ｃａ）＋（Ｃｂ）２〜３；Ｄ）モリブデン酸アンモニウムをモリブデン元素換算で０．０１〜０．１％；Ｅ）バナジウム化合物をバナジウム元素換算で０．１〜１．０％；Ｆ）フッ素含有チタン化合物をチタン元素換算で０．１〜５％；並びに、Ｇ）リン化合物をリン元素換算で０．０１〜０．５％含む。上記表面処理鋼板の外観はアルカリ性脱脂剤によって損なわれないが、この処理方法では、アルカリ洗浄後の鋼板の耐腐食性を完全に保証することができない。なぜなら、実際、家電製品部品及びマイクロモーターなどはほとんどが露出しており、非常に高い鋼板の耐腐食性が求められるからである。したがって、上記亜鉛めっき鋼板の性能は、対応する基準を満たすことができない。 Patent Document 3 (publication date: July 28, 2010, name: “galvanized steel sheet and surface treatment agent having excellent workability, alkali resistance and solvent resistance”) is a zinc whose surface is coated with an organic composite protective film. It relates to a plated steel sheet. The galvanized steel sheet comprises A) a cationic polyurethane resin having an elongation of 20 to 100% and a glass transition temperature of 50 to 100 ° C .; B) a polyethylene oxide having a particle diameter (median diameter) of 1 to 2 μm. 5-10% of the particles; C) one or more organosilane coupling agents (Ca) containing one or more amino functional groups containing at least one active hydrogen and one containing at least one epoxy functional group The above organosilane coupling agent (Cb) is in a weight ratio (Ca) / (Cb) of 0.2 to 0.4, and the weight ratio of the total amount of the cationic polyurethane resin (A) to the total amount of the organosilane coupling agent ( A) / (Ca) + (Cb) 2 to 3; D) 0.01 to 0.1% of ammonium molybdate in terms of molybdenum element; E) Vanadium compound in an amount of 0. ~1.0%; F) 0.1~5% of fluorine-containing titanium compound in the titanium element in terms; and comprises 0.01-0.5% by terms of phosphorus to G) phosphorus compounds. Although the external appearance of the surface-treated steel sheet is not impaired by the alkaline degreasing agent, this treatment method cannot completely guarantee the corrosion resistance of the steel sheet after alkali cleaning. This is because, in fact, most home appliance parts and micromotors are exposed, and very high corrosion resistance of the steel sheet is required. Therefore, the performance of the galvanized steel sheet cannot satisfy the corresponding standard.
上記特許文献で開示された鋼板の表面に形成された膜層は、２回の被覆、２回の焼き付けによって得られるものであるか、あるいは、該膜層で被覆された鋼板が所定の性能要件を満たさないものである。この観点から、被覆した鋼板がより良好な性能パラメータを有し、且つ、表面処理剤を鋼板に被覆する処理工程を簡素化できる鋼板被覆用表面処理剤を求めるビジネスニーズがある。 The film layer formed on the surface of the steel sheet disclosed in the above patent document is obtained by two coatings and two bakings, or the steel sheet coated with the film layer has predetermined performance requirements. Is not satisfied. From this point of view, there is a business need for a steel sheet coating surface treatment agent that has a better performance parameter and that can simplify the treatment process of coating the steel sheet with the surface treatment agent.
本発明の目的は、亜鉛めっき鋼板用表面処理剤を提供することである。この環境負荷の小さい表面処理剤で被覆した亜鉛めっき鋼板は、優れた加工性、優れた耐腐食性及び良好な塗装性を有する。また、この環境負荷の小さい表面処理剤はクロムを含まない。 The object of the present invention is to provide a surface treating agent for galvanized steel sheet. The galvanized steel sheet coated with the surface treatment agent having a small environmental load has excellent workability, excellent corrosion resistance, and good paintability. Moreover, this surface treatment agent with a small environmental load does not contain chromium.
上記目的を達成するため、本発明は、環境負荷の小さい亜鉛めっき鋼板用表面処理剤を提供する。その水溶液は以下の質量部の固体成分：
封鎖型変性カチオン性ポリウレタン樹脂Ａ３０〜５５部；
少なくとも１個の活性水素アミノ官能基を含む有機シランカップリング剤Ｂ１と、少なくとも１個のエポキシ官能基を含む有機シランカップリング剤Ｂ２とを含み、Ｂ１／Ｂ２比が０．４〜１であるシランカップリング剤Ｂ３２〜６０部；
表面グラフト化高密度ポリエチレン粒子又は表面グラフト化ポリアミド粒子Ｃ３〜１５部；
バナジウム元素換算でバナジウム含有化合物Ｄ０．０１〜０．５部：
リン元素換算でリン含有化合物Ｅ０．５〜１．５部；
チタン元素換算でフッ素含有チタン化合物Ｆ０．１〜１部；及び、
セリウム元素換算でセリウム含有化合物Ｇ０．０１〜１部
を含む。
In order to achieve the above object, the present invention provides a surface treating agent for a galvanized steel sheet having a low environmental load. The aqueous solution has the following solid parts in mass parts
30-55 parts of a blocking-type modified cationic polyurethane resin A;
An organic silane coupling agent B1 containing at least one active hydrogen amino functional group and an organic silane coupling agent B2 containing at least one epoxy functional group, with a B1 / B2 ratio of 0.4-1 Silane coupling agent B32-60 parts;
3 to 15 parts of surface grafted high density polyethylene particles or surface grafted polyamide particles;
Vanadium-containing compound D 0.01 to 0.5 parts in terms of vanadium element:
Phosphorus-containing compound E 0.5 to 1.5 parts in terms of phosphorus element;
Fluorine-containing titanium compound F0.1-1 part in terms of titanium element; and
Contains 0.01 to 1 part of cerium-containing compound G in terms of cerium element.
上記技術スキームにおいて、封鎖型変性カチオン性ポリウレタン樹脂Ａの量を３０〜５５部に調節するのは、次のような理由からである。該固体成分の量が３０部未満であると、得られる皮膜の延性及び耐摩耗性が低下するとともに、皮膜と他の有機塗膜との塗膜密着性も低下する。該固体成分の量が５５部を超えると、得られる皮膜と亜鉛めっき鋼板との密着性及び耐腐食性が低下する場合がある。 In the above technical scheme, the amount of the blocked modified cationic polyurethane resin A is adjusted to 30 to 55 parts for the following reason. When the amount of the solid component is less than 30 parts, the ductility and wear resistance of the resulting film are lowered, and the adhesion between the film and another organic coating film is also lowered. When the amount of the solid component exceeds 55 parts, the adhesion between the obtained film and the galvanized steel sheet and the corrosion resistance may decrease.
ここで、上記水溶液中の封鎖型変性カチオン性ポリウレタン樹脂Ａは、水溶液又は水分散性型であってもよい。 Here, the blocked modified cationic polyurethane resin A in the aqueous solution may be an aqueous solution or a water-dispersible type.
なお、高密度ポリエチレンとは、配位重合によって形成され、密度が９４１ｋｇ／ｍ３〜９６０ｋｇ／ｍ３であり、結晶性が高く、分子鎖が規則的に配列したポリエチレンのことを言う。 The high density polyethylene refers to polyethylene that is formed by coordination polymerization, has a density of 941 kg / m 3 to 960 kg / m 3 , has high crystallinity, and molecular chains are regularly arranged.
有機シランカップリング剤Ｂ１及び有機シランカップリング剤Ｂ２は、水溶液中で部分的に事前合成される。この事前合成シラン化合物によって、平面方向の皮膜の架橋度を高めて、皮膜の耐摩耗性を向上させ、皮膜の耐腐食性を高めることができる。一方、事前合成シラン化合物中に残る活性基は、鋼板表面と反応して、皮膜と鋼板界面との密着性を高めることができる。シランカップリング剤Ｂの量を３２〜６０部に調節する理由は、この成分の量が３２部未満であると、事前合成後のシラン中の残る活性基の量が鋼板との反応に必要な量よりも少なくなり、皮膜の密着性及び耐腐食性が低下し、一方、この成分の量が６０部を超えると、シラン含有量が多くなりすぎて、架橋密度が高くなりすぎ、その結果、皮膜の延性が大幅に低下するからである。 The organosilane coupling agent B1 and the organosilane coupling agent B2 are partially pre-synthesized in an aqueous solution. With this pre-synthetic silane compound, the degree of cross-linking of the film in the plane direction can be increased, the wear resistance of the film can be improved, and the corrosion resistance of the film can be increased. On the other hand, the active groups remaining in the pre-synthetic silane compound can react with the surface of the steel sheet to enhance the adhesion between the coating and the steel sheet interface. The reason for adjusting the amount of the silane coupling agent B to 32 to 60 parts is that when the amount of this component is less than 32 parts, the amount of remaining active groups in the silane after the pre-synthesis is necessary for the reaction with the steel plate. Less than the amount, and the adhesion and corrosion resistance of the film is reduced, while when the amount of this component exceeds 60 parts, the silane content becomes too high and the crosslinking density becomes too high. This is because the ductility of the film is greatly reduced.
本発明の技術的解決法に用いられる表面グラフト化高密度ポリエチレン粒子又は表面グラフト化ポリアミド粒子Ｃは、固体潤滑剤であり、皮膜との間に高い界面結合強度を提供し、腐食性媒体が固体潤滑剤の界面に沿って皮膜内に浸透するのを遅らせ、固体潤滑剤の添加が皮膜の耐腐食性に及ぼす負の影響を低下させる。表面グラフト化高密度ポリエチレン粒子又は表面グラフト化ポリアミド粒子Ｃの量は３〜１５重量部に調節しなければならない。この量が３部未満であると、皮膜の表面潤滑性及び耐摩耗性が充分ではない。この量が１５部を超えると、皮膜中の粒子が多くなりすぎて、表面グラフト化高密度ポリエチレン粒子又は表面グラフト化ポリアミド粒子によって形成された界面に沿って腐食性媒体が皮膜内に浸透する可能性があり、これによって皮膜の耐腐食性及び耐溶剤性が低下する。 The surface-grafted high-density polyethylene particles or the surface-grafted polyamide particles C used in the technical solution of the present invention are solid lubricants, provide high interfacial bond strength with the coating, and the corrosive medium is solid. Delays penetration into the coating along the lubricant interface and reduces the negative impact of solid lubricant addition on the corrosion resistance of the coating. The amount of surface grafted high density polyethylene particles or surface grafted polyamide particles C should be adjusted to 3-15 parts by weight. When this amount is less than 3 parts, the surface lubricity and wear resistance of the film are not sufficient. If this amount exceeds 15 parts, there will be too many particles in the coating and the corrosive medium can penetrate into the coating along the interface formed by the surface grafted high density polyethylene particles or the surface grafted polyamide particles. This reduces the corrosion resistance and solvent resistance of the coating.
バナジウム含有化合物Ｄのバナジウム元素換算量を０．０１〜０．５部に調節する理由は、この量が０．０１部未満であると、皮膜の耐腐食性が低下する場合があり、この量が０．５部を超えると、皮膜の密着性が悪化しやすくなるからである。 The reason for adjusting the vanadium element conversion amount of the vanadium-containing compound D to 0.01 to 0.5 part is that if this amount is less than 0.01 part, the corrosion resistance of the film may be lowered. This is because if the content exceeds 0.5 parts, the adhesion of the film tends to deteriorate.
ここで、バナジウム含有化合物Ｄのバナジウムの原子価は＋２〜＋５の範囲のいずれであってもよい。バナジウム含有化合物Ｄは、バナジウム含有酸化物（例えば酸化バナジウム（＋５）、酸化バナジウム（＋３）など）であってもよく、フッ化物塩（例えばフッ化バナジウム（＋４）、フッ化バナジウム（＋５）など）であってもよい。 Here, the valence of vanadium of the vanadium-containing compound D may be in the range of +2 to +5. The vanadium-containing compound D may be a vanadium-containing oxide (eg, vanadium oxide (+5), vanadium oxide (+3), etc.), or a fluoride salt (eg, vanadium fluoride (+4), vanadium fluoride (+5), etc.) ).
リン含有化合物Ｅ中のリン元素換算で、リン元素量が０．５部未満であると、リン元素の添加効果は顕著ではなく、皮膜の耐腐食性が低下する場合がある。リン元素量が１．５部を超えると、皮膜の密着性が悪化しやすくなる。 If the amount of phosphorus element is less than 0.5 parts in terms of phosphorus element in phosphorus-containing compound E, the effect of adding phosphorus element is not significant, and the corrosion resistance of the film may be reduced. When the amount of phosphorus element exceeds 1.5 parts, the adhesion of the film tends to deteriorate.
なお、リン含有化合物Ｅはリン酸又はアンモニウム塩として用意してもよい。 The phosphorus-containing compound E may be prepared as phosphoric acid or an ammonium salt.
本発明の技術的解決法では、フッ素含有チタン化合物Ｆの量も調節する必要がある。フッ素含有チタン化合物中のチタン元素換算でチタン元素量が０．１部未満であると、何の効果も得られず、皮膜の密着性が悪化する場合がある。チタン元素量が１．０部を超えると、処理剤の安定性が悪化し、その結果、亜鉛めっき鋼板の表面処理品質に影響を及ぼす。 In the technical solution of the present invention, it is also necessary to adjust the amount of the fluorine-containing titanium compound F. If the amount of titanium element is less than 0.1 part in terms of titanium element in the fluorine-containing titanium compound, no effect can be obtained and the adhesion of the film may deteriorate. When the amount of titanium element exceeds 1.0 part, the stability of the treatment agent is deteriorated, and as a result, the surface treatment quality of the galvanized steel sheet is affected.
セリウム含有化合物Ｇは、亜鉛めっき鋼板の表面亜鉛めっき層と反応し、上記水溶液中のシランカップリング剤Ｂの加水分解後にヒドロキシル反応を起こして、高い結合エネルギーを有する−Ｃｅ−Ｏ−Ｚｎ−結合及び−Ｃｅ−Ｏ−Ｓｉ−結合を形成することができる。したがって、薄く、構造的に緻密なセリウム塩変換膜が亜鉛めっき層の表面に形成され、このため、鋼板が腐食性媒体に直接接触するのが物理的に遮断され、鋼板の腐食の可能性が低減し、鋼板が塗膜下腐食に耐える能力が大幅に向上する。同時に、セリウム塩変換膜とシランカップリング剤Ｂとの反応によって形成された−Ｃｅ−Ｏ−Ｓｉ−結合は、皮膜の密着性を向上させ、剥離摩擦の過程で皮膜が剥離するのを防止することができる。セリウム元素換算量が０．０１部未満であると、添加効果が得られず、皮膜の耐腐食性及び密着性が低下する場合がある。セリウム元素換算で化合物の量が１部を超えると、処理剤の安定性が悪化し、亜鉛めっき鋼板の表面処理品質に影響を及ぼす場合がある。 The cerium-containing compound G reacts with the surface galvanized layer of the galvanized steel sheet, causes hydroxyl reaction after hydrolysis of the silane coupling agent B in the aqueous solution, and has a high binding energy -Ce-O-Zn- bond And -Ce-O-Si- bonds can be formed. Therefore, a thin and structurally dense cerium salt conversion film is formed on the surface of the galvanized layer, and thus the steel sheet is physically blocked from directly contacting the corrosive medium, and the steel sheet may be corroded. And the ability of the steel sheet to withstand corrosion under the coating is greatly improved. At the same time, the -Ce-O-Si- bond formed by the reaction between the cerium salt conversion film and the silane coupling agent B improves the adhesion of the film and prevents the film from peeling in the process of peeling friction. be able to. When the cerium element conversion amount is less than 0.01 part, the effect of addition cannot be obtained, and the corrosion resistance and adhesion of the film may be lowered. When the amount of the compound exceeds 1 part in terms of cerium element, the stability of the treatment agent is deteriorated and the surface treatment quality of the galvanized steel sheet may be affected.
ここで、セリウム含有化合物Ｇのセリウムの原子価は＋３又は＋４のいずれであってもよい。セリウム含有化合物Ｇは、硝酸セリウム、硫酸セリウム、フッ素含有セリウム塩又はセリウムアンモニウム錯塩の１種以上であってもよい。 Here, the valence of cerium of the cerium-containing compound G may be either +3 or +4. The cerium-containing compound G may be one or more of cerium nitrate, cerium sulfate, fluorine-containing cerium salt, or cerium ammonium complex salt.
さらに、本発明に係る環境負荷の小さい亜鉛めっき鋼板用表面処理剤において、封鎖型変性カチオン性ポリウレタン樹脂Ａは、有機化合物により末端封鎖変性されており、上記有機化合物は、エポキシ樹脂Ｅ−４４、ヒドロキシシロキサン又はアクリル酸ヒドロキシエチルである。 Furthermore, in the surface treating agent for a galvanized steel sheet having a low environmental load according to the present invention, the blocking-type modified cationic polyurethane resin A is end-blocked by an organic compound, and the organic compound is an epoxy resin E-44, Hydroxysiloxane or hydroxyethyl acrylate.
封鎖型変性カチオン性ポリウレタン樹脂Ａの末端封鎖変性に使用される有機化合物は、具体的には、エポキシ樹脂Ｅ−４４、ヒドロキシシロキサン又はアクリル酸ヒドロキシエチルの何れかである。使用される有機化合物は、エポキシ基、エステル基又は水酸基などの活性基を１種有するので、該有機化合物は、シランカップリング剤Ｂ及び表面グラフト化高密度ポリエチレン粒子又は表面グラフト化ポリアミド粒子Ｃと反応して、皮膜の架橋度及び表面グラフト化高密度ポリエチレン粒子又は表面グラフト化ポリアミド粒子Ｃと皮膜との界面結合力を高めることにより、皮膜のスタンプ加工性及び耐摩耗性を向上させることができる。同時に、有機化合物と処理剤中の他の成分との反応により形成された基（例えばエーテル結合、カルボニル基及びエステル基など）はすべて極性基である。これらの極性基もまた、皮膜の表面極性を高めて、皮膜と他の有機塗膜との塗膜密着性を向上させることができる。 Specifically, the organic compound used for the end-capping modification of the blocking-type modified cationic polyurethane resin A is any one of epoxy resin E-44, hydroxysiloxane, or hydroxyethyl acrylate. Since the organic compound used has one kind of active group such as an epoxy group, an ester group or a hydroxyl group, the organic compound includes a silane coupling agent B and surface grafted high-density polyethylene particles or surface grafted polyamide particles C. By reacting and increasing the degree of cross-linking of the film and the interfacial bond strength between the surface-grafted high-density polyethylene particles or the surface-grafted polyamide particles C and the film, the stamp processability and wear resistance of the film can be improved. . At the same time, all groups formed by the reaction of the organic compound with other components in the treating agent (for example, ether bond, carbonyl group, ester group, etc.) are polar groups. These polar groups can also increase the surface polarity of the coating and improve the adhesion between the coating and other organic coatings.
本発明に係る環境負荷の小さい亜鉛めっき鋼板用表面処理剤において、封鎖型変性カチオン性ポリウレタン樹脂Ａの量は４０〜５０部であるのが好ましい。 In the surface treatment agent for a galvanized steel sheet having a small environmental load according to the present invention, the amount of the blocking-type modified cationic polyurethane resin A is preferably 40 to 50 parts.
さらに、本発明に係る環境負荷の小さい亜鉛めっき鋼板用表面処理剤において、封鎖型変性カチオン性ポリウレタン樹脂Ａに対するシランカップリング剤Ｂの重量比は０．７〜２．０である。 Furthermore, in the surface treating agent for a galvanized steel sheet having a small environmental load according to the present invention, the weight ratio of the silane coupling agent B to the blocking type modified cationic polyurethane resin A is 0.7 to 2.0.
封鎖型変性カチオン性ポリウレタン樹脂Ａに対するシランカップリング剤Ｂの重量比が０．７未満、すなわち封鎖型変性カチオン性ポリウレタン樹脂Ａの量が比較的多いと、皮膜の耐腐食性、密着性及び耐摩耗性が低下する場合がある。封鎖型変性カチオン性ポリウレタン樹脂Ａに対するシランカップリング剤Ｂの重量比が２．０を超える、すなわち封鎖型変性カチオン性ポリウレタン樹脂Ａの量が比較的少ないと、皮膜の延性が悪化し、鋼板のスタンプ成形時に皮膜に亀裂が生じやすく、その結果、その後の耐腐食性に影響を及ぼす。 When the weight ratio of the silane coupling agent B to the blocking-type modified cationic polyurethane resin A is less than 0.7, that is, when the amount of the blocking-type modified cationic polyurethane resin A is relatively large, the corrosion resistance, adhesion and resistance of the film are reduced. Abrasion may be reduced. When the weight ratio of the silane coupling agent B to the blocking-type modified cationic polyurethane resin A exceeds 2.0, that is, when the amount of the blocking-type modified cationic polyurethane resin A is relatively small, the ductility of the film deteriorates, The film tends to crack during stamping, and as a result, the subsequent corrosion resistance is affected.
さらに、本発明に係る環境負荷の小さい亜鉛めっき鋼板用表面処理剤において、表面グラフト化高密度ポリエチレン粒子又は表面グラフト化ポリアミド粒子Ｃの粒径（メジアン径）は０．５〜３μｍである。 Furthermore, in the surface treating agent for a galvanized steel sheet having a small environmental load according to the present invention, the particle diameter (median diameter) of the surface-grafted high-density polyethylene particles or the surface-grafted polyamide particles C is 0.5 to 3 μm.
表面グラフト化高密度ポリエチレン粒子又は表面グラフト化ポリアミド粒子Ｃの粒径は、環境負荷の小さい表面処理剤で被覆した亜鉛めっき鋼板の全体的性能がより良くなるように設定しなければならない。粒径が０．５μｍ未満であると、粒子は表面グラフト化後に凝集しやすく、水系に分散しにくくなり、また、皮膜に添加しても潤滑作用が得られない。粒径が３μｍを超える、すなわち、粒径が皮膜の厚みよりも大きいと、粒子の大部分は皮膜の表面に露出する。したがって、スタンプ時の摩擦に曝されると、大きい粒子ほど剥離しやすくなり、それにより皮膜のスタンプ加工性が急激に低下する。 The particle size of the surface-grafted high-density polyethylene particles or the surface-grafted polyamide particles C must be set so that the overall performance of the galvanized steel sheet coated with the surface treatment agent having a small environmental load is improved. If the particle size is less than 0.5 μm, the particles are likely to aggregate after surface grafting, become difficult to disperse in an aqueous system, and even if added to a film, a lubricating action cannot be obtained. When the particle diameter exceeds 3 μm, that is, when the particle diameter is larger than the thickness of the film, most of the particles are exposed on the surface of the film. Therefore, when exposed to the friction during stamping, larger particles are more likely to be peeled off, thereby rapidly reducing the stamp processability of the coating.
表面グラフト化高密度ポリエチレン粒子又は表面グラフト化ポリアミド粒子Ｃの粒径（メジアン径）は１．２〜２μｍであることが好ましい。 The particle diameter (median diameter) of the surface grafted high density polyethylene particles or the surface grafted polyamide particles C is preferably 1.2 to 2 μm.
さらに、本発明に係る環境負荷の小さい亜鉛めっき鋼板用表面処理剤において、表面グラフト化高密度ポリエチレン粒子又は表面グラフト化ポリアミド粒子Ｃは、表面が反応性活性基でグラフト化されており、上記反応性活性基は、エポキシ基、アミノ基及びカルバメート基のうちの少なくとも１種である。 Further, in the surface treatment agent for galvanized steel sheet with a low environmental load according to the present invention, the surface grafted high-density polyethylene particles or the surface grafted polyamide particles C have a surface grafted with reactive active groups, and the above reaction The active group is at least one of an epoxy group, an amino group, and a carbamate group.
上記反応性活性基は、処理剤中の封鎖型変性カチオン性ポリウレタン樹脂Ａ及びシランカップリング剤Ｂと反応して共有結合を形成することができる。また、表面グラフト化高密度ポリエチレン粒子又は表面グラフト化ポリアミド粒子Ｃと皮膜との界面結合強度を高めながら、表面グラフト化高密度ポリエチレン粒子又は表面グラフト化ポリアミド粒子Ｃに結合することにより、皮膜表面へ蓄積するのを防止して、皮膜中に確実に均一に分散させて、皮膜の表面潤滑性能を高めるとともに、皮膜の厚み方向全体に亘って優れた耐摩耗性を提供し、これにより皮膜のスタンプ加工性及び耐摩耗性を向上させることができる。また、表面グラフト化高密度ポリエチレン粒子又は表面グラフト化ポリアミド粒子Ｃは皮膜の表面に存在するため、皮膜の表面極性を向上させるだけでなく、表面グラフト化高密度ポリエチレン粒子又は表面グラフト化ポリアミド粒子Ｃの添加が皮膜の塗工性に及ぼす悪影響を低減することもできる。 The reactive active group can react with the blocking-type modified cationic polyurethane resin A and the silane coupling agent B in the treating agent to form a covalent bond. Further, by increasing the interfacial bond strength between the surface-grafted high-density polyethylene particles or the surface-grafted polyamide particles C and the film, the surface-grafted high-density polyethylene particles or the surface-grafted polyamide particles C are bonded to the surface of the film. Prevents accumulation and ensures uniform distribution in the coating, improving the surface lubrication performance of the coating and providing excellent wear resistance throughout the thickness of the coating, thereby providing a stamp on the coating Workability and wear resistance can be improved. Further, since the surface-grafted high-density polyethylene particles or the surface-grafted polyamide particles C are present on the surface of the film, not only the surface polarity of the film is improved, but also the surface-grafted high-density polyethylene particles or the surface-grafted polyamide particles C It is also possible to reduce the adverse effect of the addition of on the coatability of the film.
好ましい実施形態では、表面グラフト化高密度ポリエチレン粒子又は表面グラフト化ポリアミド粒子Ｃの量は６〜１２重量部である。 In a preferred embodiment, the amount of surface grafted high density polyethylene particles or surface grafted polyamide particles C is 6-12 parts by weight.
本発明に係る環境負荷の小さい亜鉛めっき鋼板用表面処理剤において、セリウム含有化合物Ｇのセリウム元素換算量は０．２〜０．６質量部であることが好ましい。 In the surface treatment agent for a galvanized steel sheet having a small environmental load according to the present invention, the cerium-containing compound G preferably has a cerium element equivalent amount of 0.2 to 0.6 parts by mass.
なお、本発明に係る環境負荷の小さい亜鉛めっき鋼板用表面処理剤で被覆される亜鉛めっき鋼板の寸法及び形状は特に限定されない。 In addition, the dimension and shape of the galvanized steel sheet coated with the surface treatment agent for galvanized steel sheet with a small environmental load according to the present invention are not particularly limited.
本発明の別の目的は、亜鉛めっき鋼板を提供することである。この亜鉛めっき鋼板は、優れた加工性、すなわちスタンプ加工後の良好な外観及び鋼板表面の良好な耐摩耗性を有する。また、この亜鉛めっき鋼板は、優れた耐腐食性、すなわち鋼板の良好な平板耐腐食性、スタンプ成形後の良好な耐腐食性及びアルカリ性脱脂剤による洗浄処理後の良好な耐腐食性を有する。さらに、この亜鉛めっき鋼板は、良好な塗装性、すなわちアルキド樹脂塗料、エポキシ粉末塗料及びポリウレタン断熱発泡体に対する良好な塗膜密着性を有する。同時に、この亜鉛めっき鋼板は、様々な薬品に対する良好な耐性、例えば良好な耐アルカリ性及び良好な耐溶剤性を有する。 Another object of the present invention is to provide a galvanized steel sheet. This galvanized steel sheet has excellent workability, that is, good appearance after stamping and good wear resistance of the steel sheet surface. Moreover, this galvanized steel sheet has excellent corrosion resistance, that is, good flat plate corrosion resistance of the steel sheet, good corrosion resistance after stamping, and good corrosion resistance after washing with an alkaline degreasing agent. Furthermore, this galvanized steel sheet has good paintability, that is, good coating film adhesion to alkyd resin paints, epoxy powder paints and polyurethane heat insulating foams. At the same time, the galvanized steel sheet has good resistance to various chemicals, such as good alkali resistance and good solvent resistance.
上記目的を達成するために、本発明は、上記環境負荷の小さい亜鉛めっき鋼板用表面処理剤の何れか１種を被覆して形成された複合膜を表面に有する亜鉛めっき鋼板を提供する。 In order to achieve the above object, the present invention provides a galvanized steel sheet having on its surface a composite film formed by coating any one of the above-described surface treatment agents for galvanized steel sheet with a low environmental load.
複合膜（乾燥膜）の厚みは１〜３μｍであることが好ましい。 The thickness of the composite film (dry film) is preferably 1 to 3 μm.
複合膜の厚みは、以下の理由から１〜３μｍに調節される。複合膜の厚みが１μｍ未満であると、皮膜が薄いためスタンプ加工性及び耐腐食性が低下する場合がある。複合膜の厚みが３μｍを超えると、鋼板の単位面積あたりの表面処理コストが増加する。 The thickness of the composite film is adjusted to 1 to 3 μm for the following reasons. When the thickness of the composite film is less than 1 μm, the stamp processability and the corrosion resistance may be deteriorated because the film is thin. When the thickness of the composite film exceeds 3 μm, the surface treatment cost per unit area of the steel sheet increases.
本発明のさらなる目的は、亜鉛めっき鋼板の製造方法を提供することである。この製造方法によって得られた亜鉛めっき鋼板は、環境負荷の小さい水性処理剤で表面が被覆されており、優れた加工性、優れた耐腐食性及び良好な塗装性を示す。 A further object of the present invention is to provide a method for producing a galvanized steel sheet. The surface of the galvanized steel sheet obtained by this production method is coated with an aqueous treatment agent having a small environmental load, and exhibits excellent workability, excellent corrosion resistance, and good paintability.
上記目的を達成するために、本発明は、亜鉛めっき鋼板の製造方法であって、亜鉛めっき鋼板の表面を環境負荷の小さい亜鉛めっき鋼板用表面処理剤で被覆する工程と、８０〜１８０℃の温度で乾燥して上記亜鉛めっき鋼板の表面に複合膜を形成する工程とを含む製造方法を提供する。 In order to achieve the above object, the present invention is a method for producing a galvanized steel sheet, the step of coating the surface of a galvanized steel sheet with a surface treatment agent for a galvanized steel sheet having a low environmental load, And a step of drying at a temperature to form a composite film on the surface of the galvanized steel sheet.
加熱及び乾燥温度が８０℃未満であると、皮膜の架橋が充分ではなく、皮膜の性能が低下する場合がある。加熱及び乾燥温度が１８０℃を超えると、処理剤中の固体成分の性能が変化し、その結果、皮膜の成膜効果に影響が及ぼされる。 When the heating and drying temperature is less than 80 ° C., the film is not sufficiently crosslinked, and the film performance may be deteriorated. When the heating and drying temperature exceeds 180 ° C., the performance of the solid component in the treatment agent changes, and as a result, the film forming effect of the film is affected.
他の実施形態では、亜鉛めっき鋼板の製造方法は、亜鉛めっき鋼板の表面を環境負荷の小さい亜鉛めっき鋼板用表面処理剤で被覆する工程と、８０〜１８０℃の温度で乾燥して上記亜鉛めっき鋼板の表面に厚みが１〜３μｍの複合膜を形成する工程とを含む。 In another embodiment, the method for producing a galvanized steel sheet includes the steps of coating the surface of a galvanized steel sheet with a surface treatment agent for a galvanized steel sheet having a low environmental load, and drying the galvanized steel sheet at a temperature of 80 to 180 ° C. Forming a composite film having a thickness of 1 to 3 μm on the surface of the steel sheet.
また、亜鉛めっき鋼板の製造方法では、環境負荷の小さい表面処理剤を用いて、亜鉛めっき鋼板の表面に１回の被覆（例えばロールコーティング）によって複合膜を形成してもよい。従来の２回の被覆＋２回の焼き付けに比べて、本発明の表面処理剤の被覆工程は、本発明の環境負荷の小さい表面処理剤を用いることによって、より簡単になり、実行しやすく、製造設備に対する要求がより低くなる。 Moreover, in the manufacturing method of a galvanized steel plate, you may form a composite film by one coating | cover (for example, roll coating) on the surface of a galvanized steel plate using the surface treating agent with small environmental impact. Compared with the conventional two times coating + two times baking, the coating process of the surface treatment agent of the present invention becomes easier and easier to carry out by using the surface treatment agent of the present invention with less environmental impact. The demand for equipment is lower.
亜鉛めっき鋼板の製造方法では、亜鉛めっき鋼板の表面を被覆する環境負荷の小さい表面処理剤の加熱及び乾燥方法は特に限定されず、熱風加熱、誘導加熱、赤外線加熱などの様々な加熱方法であってもよい。 In the method for producing a galvanized steel sheet, the heating and drying method of the surface treatment agent with a low environmental load that covers the surface of the galvanized steel sheet is not particularly limited, and there are various heating methods such as hot air heating, induction heating, and infrared heating. May be.
本発明に係る環境負荷の小さい亜鉛めっき鋼板用表面処理剤で被覆した亜鉛めっき鋼板は、優れた加工性、良好な耐腐食性及び良好な塗装性を有する。 The galvanized steel sheet coated with the surface treatment agent for a galvanized steel sheet having a small environmental load according to the present invention has excellent workability, good corrosion resistance and good paintability.
また、本発明に係る環境負荷の小さい亜鉛めっき鋼板用表面処理剤で被覆した亜鉛めっき鋼板は、耐アルカリ性又は耐溶剤性など、様々な薬品に対する耐性が向上している。 In addition, the galvanized steel sheet coated with the surface treatment agent for galvanized steel sheet having a low environmental load according to the present invention has improved resistance to various chemicals such as alkali resistance or solvent resistance.
また、本発明に係る環境負荷の小さい亜鉛めっき鋼板用表面処理剤はクロムを含まないため、環境への影響が小さい。上記処理剤及びその処理剤で被覆した亜鉛めっき鋼板は、環境負荷がより小さく、より経済的である。 Moreover, since the surface treatment agent for galvanized steel sheets with a small environmental load according to the present invention does not contain chromium, the environmental impact is small. The treatment agent and the galvanized steel sheet coated with the treatment agent have a smaller environmental load and are more economical.
環境負荷の小さい亜鉛めっき鋼板用表面処理剤は、良好な加工性及び安定性を有する。 The surface treating agent for galvanized steel sheet having a small environmental load has good workability and stability.
本発明に係る亜鉛めっき鋼板は、優れた加工性、優れた耐腐食性、良好な塗装性及び向上した耐性を有する。 The galvanized steel sheet according to the present invention has excellent workability, excellent corrosion resistance, good paintability and improved resistance.
また、本発明に係る亜鉛めっき鋼板の表面の被覆膜はクロムを含まない。 Moreover, the coating film on the surface of the galvanized steel sheet according to the present invention does not contain chromium.
また、本発明に係る亜鉛めっき鋼板の製造方法は処理工程が少なく、実行しやすい。 Moreover, the manufacturing method of the galvanized steel sheet which concerns on this invention has few process steps, and is easy to implement.
以下、本発明に係る環境負荷の小さい亜鉛めっき鋼板用表面処理剤、亜鉛めっき鋼板及び亜鉛めっき鋼板の製造方法を具体例を参照しながらさらに説明及び例示する。しかしながら、この説明及び例示は本発明の技術的解決法に不当な限定となるものではない。 Hereinafter, the surface treatment agent for a galvanized steel sheet, a galvanized steel sheet, and a method for producing a galvanized steel sheet according to the present invention will be further described and exemplified with reference to specific examples. However, this description and illustration are not unduly limiting to the technical solutions of the present invention.
実施例１〜５及び比較例１〜３ Examples 1-5 and Comparative Examples 1-3
実施例１〜５及び比較例１〜３の基板は、厚みが０．５ｍｍの亜鉛めっき鋼板であり、亜鉛層の重量が４０／４０ｇ／ｍ２である。まず、鋼板の表面を中程度のアルカリ性の脱脂剤（ｐＨ：１１〜１２）でスプレー洗浄し、次いで純水で洗浄して表面に残留するアルカリ性成分を除去した。亜鉛めっき鋼板の表面を環境負荷の小さい亜鉛めっき鋼板用表面処理剤で被覆して、８０〜１８０℃で乾燥して、亜鉛めっき鋼板の表面に厚みが１〜３μｍの複合膜を形成した。 The substrates of Examples 1 to 5 and Comparative Examples 1 to 3 are galvanized steel sheets having a thickness of 0.5 mm, and the weight of the zinc layer is 40/40 g / m 2 . First, the surface of the steel plate was spray washed with a medium alkaline degreasing agent (pH: 11 to 12), and then washed with pure water to remove alkaline components remaining on the surface. The surface of the galvanized steel sheet was coated with a surface treatment agent for a galvanized steel sheet having a small environmental load and dried at 80 to 180 ° C. to form a composite film having a thickness of 1 to 3 μm on the surface of the galvanized steel sheet.
実施例１〜５及び比較例１〜３の環境負荷の小さい亜鉛めっき鋼板用表面処理剤中の各固体成分の質量部を表１に示す。 Table 1 shows parts by mass of each solid component in the surface-treating agent for galvanized steel sheet having a small environmental load in Examples 1 to 5 and Comparative Examples 1 to 3.
Ａ１は封鎖型変性カチオン性ポリウレタン樹脂Ａである。
Ｂ１−１はアミノプロピルトリエトキシシラン、Ｂ２−１はグリシドキシプロピルトリメトキシシラン、Ｂ１−２はアミノエチルアミノプロピルトリメトキシシラン、Ｂ２−２はグリシドキシプロピルトリエトキシシランである。
Ｃ１は表面グラフト化高密度ポリエチレン、Ｃ２は表面グラフト化ポリアミドである。
Ｄ１はメタバナジン酸アンモニウム、Ｄ２はホスホモリブドバナジン酸である。
Ｅ１はリン酸、Ｅ２はリン酸アンモニウムである。
Ｆ１はフルオロチタン酸アンモニウム、Ｆ２はヘキサフルオロチタン酸である。
Ｇ１は硝酸アンモニウムセリウム、Ｇ２は硝酸セリウムである。
A1 is a blocking type modified cationic polyurethane resin A.
B1-1 is aminopropyltriethoxysilane, B2-1 is glycidoxypropyltrimethoxysilane, B1-2 is aminoethylaminopropyltrimethoxysilane, and B2-2 is glycidoxypropyltriethoxysilane.
C1 is a surface grafted high density polyethylene and C2 is a surface grafted polyamide.
D1 is ammonium metavanadate and D2 is phosphomolybdovanadate.
E1 is phosphoric acid and E2 is ammonium phosphate.
F1 is ammonium fluorotitanate and F2 is hexafluorotitanic acid.
G1 is ammonium cerium nitrate, and G2 is cerium nitrate.
実施例１〜５及び比較例１〜３の乾燥温度並びに亜鉛めっき鋼板表面に形成された複合膜の厚みを表２に示す。 Table 2 shows the drying temperatures of Examples 1 to 5 and Comparative Examples 1 to 3 and the thickness of the composite film formed on the surface of the galvanized steel sheet.
以下の試験方法に従って、実施例１〜５及び比較例１〜３の環境負荷の小さい亜鉛めっき鋼板用表面処理剤で被覆した亜鉛めっき鋼板の試料を採取し、試験した。これらのそれぞれの性能を評価するために得た試験データを表３に示す。表中、性能パラメータ評価試験は以下のように説明される。 According to the following test method, the sample of the galvanized steel plate coat | covered with the surface treating agent for Examples 1-5 and comparative examples 1-3 with a small environmental load for galvanized steel plates was extract | collected and tested. Table 3 shows the test data obtained for evaluating each of these performances. In the table, the performance parameter evaluation test is explained as follows.
１）平板耐腐食性：
ＡＳＴＭ Ｂ１１７に従って試験時間１２０時間で平板の塩水スプレー試験を行った。評価基準は以下の通りである。
◎：白錆面積率が５％未満
○：白錆面積率が５％超１０％未満
△：白錆面積率が１０％超５０％未満
×：白錆面積率が５０％超
1) Flat plate corrosion resistance:
A flat plate salt spray test was conducted at a test time of 120 hours in accordance with ASTM B117. The evaluation criteria are as follows.
◎: White rust area ratio is less than 5% ○: White rust area ratio is more than 5% and less than 10% △: White rust area ratio is more than 10% and less than 50% ×: White rust area ratio is more than 50%
２）成形後の耐腐食性
１．ＡＳＴＭ Ｂ１１７に従って、エリクセンカッピング試験機（８ｍｍカッピング用）を用いてカッピング部分の塩水スプレー試験を行った。試験時間は７２時間であった。評価基準は以下の通りである。
◎：カッピング部分の白錆面積率が５％未満
○：カッピング部分の白錆面積率が５％超１０％未満
△：カッピング部分の白錆面積率が１０％超５０％未満
×：カッピング部分の白錆面積率が５０％超
2) Corrosion resistance after molding In accordance with ASTM B117, a salt spray test of the cupping portion was performed using an Erichsen cupping tester (for 8 mm cupping). The test time was 72 hours. The evaluation criteria are as follows.
A: The white rust area ratio of the cupping part is less than 5%. A: The white rust area ratio of the cupping part is more than 5% and less than 10%. Δ: The white rust area ratio of the cupping part is more than 10% and less than 50%. White rust area ratio is over 50%
２．深絞り法により試料を作製した。実験の条件：固定ビード下圧力３ｋＮ、圧力ヘッド直径９．６ｍｍ、深絞り速度２００ｍｍ／分。ＡＳＴＭ Ｂ１１７に従って試験時間７２時間で深絞り部分の塩水スプレー試験を行った。評価基準は以下の通りである。
◎：深絞り部分の白錆面積率が５％未満
○：深絞り部分の白錆面積率が５％超１０％未満
△：深絞り部分の白錆面積率が１０％超５０％未満
×：深絞り部分の白錆面積率が５０％超
2. A sample was prepared by a deep drawing method. Experimental conditions: pressure under fixed bead 3 kN, pressure head diameter 9.6 mm, deep drawing speed 200 mm / min. According to ASTM B117, the salt spray test of the deep-drawn portion was performed at a test time of 72 hours. The evaluation criteria are as follows.
A: White rust area ratio of deep-drawn portion is less than 5% B: White rust area ratio of deep-drawn portion is more than 5% and less than 10% Δ: White rust area ratio of deep-drawn portion is more than 10% and less than 50% x: The white rust area ratio of deep-drawn parts exceeds 50%
３）アルカリ洗浄後の耐腐食性：
中程度のアルカリ性の脱脂剤（ｐＨ：１１〜１２）で洗浄し、５０℃で３分間スプレーした。ＡＳＴＭ Ｂ１１７に従って試験時間２４０時間で洗浄後の試料の塩水スプレー試験を行った。評価基準は以下の通りである。
◎：白錆面積率が５％未満
○：白錆面積率が５％超１０％未満
△：白錆面積率が１０％超５０％未満
×：白錆面積率が５０％超
3) Corrosion resistance after alkali cleaning:
Wash with medium alkaline degreasing agent (pH: 11-12) and spray at 50 ° C. for 3 minutes. The salt spray test of the sample after washing was conducted according to ASTM B117 at a test time of 240 hours. The evaluation criteria are as follows.
◎: White rust area ratio is less than 5% ○: White rust area ratio is more than 5% and less than 10% △: White rust area ratio is more than 10% and less than 50% ×: White rust area ratio is more than 50%
４）スタンプ成形性：
深絞り方法を用いて試料を作製した。実験の条件：固定ビード下圧力３ｋＮ、圧力ヘッド直径９．６ｍｍ、深絞り速度２００ｍｍ／分。評価基準は以下の通りである。
◎：外観に変化無し
○：外観に少量の黒点
△：外観によりはっきりした黒すじ
×：外観の全面に黒色
4) Stamp formability:
Samples were prepared using the deep drawing method. Experimental conditions: pressure under fixed bead 3 kN, pressure head diameter 9.6 mm, deep drawing speed 200 mm / min. The evaluation criteria are as follows.
◎: No change in appearance ○: Small amount of black spots on appearance △: Black streaks clearly defined by appearance ×: Black on the entire appearance
５）塗装性：
被覆後、以下の条件で表面処理済み亜鉛めっき鋼板に対して塗膜密着性試験を行った。試験条件は以下である。
１．アルキド白色塗料（上海振華造漆廠製、等級：Ａ−０９）、２２＃バーコーティング、焼き付け条件：１４０℃×４０分；
２．エポキシ粉末塗料（Ａｋｚｏ Ｎｏｂｅｌ製、等級：ＥＡ０５ＢＨ）、スプレー層厚み７０〜８０μｍ、焼き付け条件：２００℃×１０分；
5) Paintability:
After coating, a coating adhesion test was performed on the surface-treated galvanized steel sheet under the following conditions. The test conditions are as follows.
1. Alkyd white paint (Shanghai Zhenhua Zushi Co., Ltd. grade: A-09), 22 # bar coating, baking conditions: 140 ° C. × 40 minutes;
2. Epoxy powder paint (Akzo Nobel, grade: EA05BH), spray layer thickness 70-80 μm, baking conditions: 200 ° C. × 10 minutes;
上記２種類の塗料の被覆後、ナイフを用いて塗膜表面に１００個の小さな格子状の切り込みを入れた。格子の寸法は１ｍｍ２で、深さは塗膜層を通って鋼板表面に達する深さであった。ガラステープで剥離した後、塗膜に残った格子の数を数えた。残った格子の数が多い程、鋼板に対するアルキド白色塗料又はエポキシ粉末塗料の塗装性能が優れている。 After coating the two types of paints, 100 small grid-like cuts were made on the surface of the coating film using a knife. The size of the lattice was 1 mm 2 and the depth was the depth that reached the steel sheet surface through the coating layer. After peeling with a glass tape, the number of lattices remaining in the coating film was counted. The greater the number of remaining grids, the better the coating performance of the alkyd white paint or epoxy powder paint on the steel sheet.
３．ポリウレタン断熱発泡体層（上海克絡蒂製）、ポリウレタンＡ材料及びＢ材料（重量比２：１）を採取した後、互いに混合し、素早く撹拌してから、試験鋼板上に注いで、鋼板上で発泡させ硬化させた。２４時間静置した後、ポリウレタン発泡体層を鋼板の表面から剥がした。剥がした跡のポリウレタン発泡体残留物の有無を観察した。残留比率が高いほど、ポリウレタン発泡体の密着性が強くなり、鋼板に対するポリウレタン発泡体の塗装性能が優れていることを示す。 3. Polyurethane heat insulation foam layer (manufactured by Shanghai Kang Jun Co., Ltd.), polyurethane A material and B material (weight ratio 2: 1) are collected, mixed with each other, stirred rapidly, then poured onto the test steel plate, Foamed and cured. After leaving still for 24 hours, the polyurethane foam layer was peeled off from the surface of the steel sheet. The presence or absence of a polyurethane foam residue was observed. The higher the residual ratio, the stronger the adhesion of the polyurethane foam, and the better the coating performance of the polyurethane foam on the steel sheet.
表３は、実施例１〜５及び比較例１〜３の環境負荷の小さい表面処理剤で被覆した亜鉛めっき鋼板の試料を試験して得られた性能パラメータを示す。 Table 3 shows performance parameters obtained by testing samples of galvanized steel sheets coated with a surface treatment agent having a small environmental load in Examples 1 to 5 and Comparative Examples 1 to 3.
表３に示すように、実施例１〜５の環境負荷の小さい表面処理剤で被覆した亜鉛めっき鋼板は、上記試験の評価で「◎」及び「○」という結果を得た。また、亜鉛めっき鋼板の塗膜及びポリウレタン発泡体層は残留割合が高く、これは、環境負荷の小さい表面処理剤で被覆した亜鉛めっき鋼板の耐腐食性（平板、成形後及びアルカリ洗浄後）、加工性及び塗装性などの総合性能が優れている又は良好であることを示している。 As shown in Table 3, the galvanized steel sheet coated with the surface treatment agent with a small environmental load of Examples 1 to 5 obtained the results of “◎” and “◯” in the evaluation of the above test. In addition, the coating film and polyurethane foam layer of the galvanized steel sheet have a high residual ratio, which means that the corrosion resistance of the galvanized steel sheet coated with a surface treatment agent with a small environmental load (after flat plate, after forming and after alkali cleaning), The overall performance such as processability and paintability is excellent or good.
表１及び表３に示されるように、実施例１〜５に比べて、比較例１の環境負荷の小さい表面処理剤中にセリウム含有化合物Ｇが存在しないため、この環境負荷の小さい表面処理剤で被覆した亜鉛めっき鋼板の深絞り後の耐腐食性及びアルカリ洗浄後の耐腐食性はいずれも劣っている。また、比較例２の環境負荷の小さい表面処理剤中の封鎖型変性カチオン性ポリウレタン樹脂Ａの量が少ないため、この環境負荷の小さい表面処理剤で被覆した亜鉛めっき鋼板の皮膜の耐腐食性は劣っており、また該亜鉛めっき鋼板に対するアルキド白色塗料、エポキシ粉末塗料及びポリウレタン断熱発泡体層の塗装性にも影響が及ぼされる。また、比較例３の環境負荷の小さい表面処理剤中の表面グラフト化高密度ポリエチレン粒子又は表面グラフト化ポリアミド粒子Ｃの量が少ないため、この環境負荷の小さい表面処理剤で被覆した亜鉛めっき鋼板はスタンプ成形性が劣っている。 As shown in Tables 1 and 3, since the cerium-containing compound G is not present in the surface treatment agent of Comparative Example 1 with a small environmental load as compared with Examples 1 to 5, this surface treatment agent with a low environmental load is present. Both the corrosion resistance after deep drawing and the corrosion resistance after alkali cleaning of the galvanized steel sheet coated with is poor. Further, since the amount of the blocking-type modified cationic polyurethane resin A in the surface treatment agent with a small environmental load in Comparative Example 2 is small, the corrosion resistance of the coating of the galvanized steel sheet coated with the surface treatment agent with a small environmental load is It is also inferior, and the paintability of the alkyd white paint, epoxy powder paint and polyurethane heat insulating foam layer on the galvanized steel sheet is also affected. Further, since the amount of the surface-grafted high-density polyethylene particles or the surface-grafted polyamide particles C in the surface treatment agent with a small environmental load of Comparative Example 3 is small, the galvanized steel sheet coated with the surface treatment agent with a small environmental load is The stamp formability is inferior.
なお、上述したものは単に本発明の特定の実施形態に過ぎず、本発明が上記実施形態に限定されず、さらに、多くの類似した変更を加えることができることは明らかである。当業者には自明であるが、本発明の開示内容から直接得られた又は想到されたすべての変更は本発明の保護範囲内である。 It should be noted that what has been described above are merely specific embodiments of the present invention, and the present invention is not limited to the above-described embodiments, and it is obvious that many similar modifications can be made. It will be apparent to those skilled in the art that all modifications obtained or conceived directly from the disclosure of the invention are within the protection scope of the invention.
Claims (12)
封鎖型変性カチオン性ポリウレタン樹脂Ａ３０〜５５部；
少なくとも１個の活性水素アミノ官能基を含む有機シランカップリング剤Ｂ１と、少なくとも１個のエポキシ官能基を含む有機シランカップリング剤Ｂ２とを含み、Ｂ１／Ｂ２比が０．４〜１であるシランカップリング剤Ｂ３２〜６０部；
表面グラフト化高密度ポリエチレン粒子又は表面グラフト化ポリアミド粒子Ｃ３〜１５部；
バナジウム元素換算でバナジウム含有化合物Ｄ０．０１〜０．５部；
リン元素換算でリン含有化合物Ｅ０．５〜１．５部；
チタン元素換算でフッ素含有チタン化合物Ｆ０．１〜１部；及び、
セリウム元素換算でセリウム含有化合物Ｇ０．０１〜１部
を含む、表面処理剤。 It is a surface treatment agent for galvanized steel sheet with a small environmental load, and its aqueous solution has the following solid parts in mass parts:
30-55 parts of a blocking-type modified cationic polyurethane resin A;
An organic silane coupling agent B1 containing at least one active hydrogen amino functional group and an organic silane coupling agent B2 containing at least one epoxy functional group, with a B1 / B2 ratio of 0.4-1 Silane coupling agent B32-60 parts;
3 to 15 parts of surface grafted high density polyethylene particles or surface grafted polyamide particles;
Vanadium-containing compound D 0.01 to 0.5 part in terms of vanadium element;
Phosphorus-containing compound E 0.5 to 1.5 parts in terms of phosphorus element;
Fluorine-containing titanium compound F0.1-1 part in terms of titanium element; and
A surface treating agent comprising 0.01 to 1 part of a cerium-containing compound G in terms of cerium element.
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| CN201510448192.7 | 2015-07-27 | ||
| PCT/CN2016/091494 WO2017016455A1 (en) | 2015-07-27 | 2016-07-25 | Environmentally friendly surface treating agent for galvanized steel sheet, galvanized steel sheet, and manufacturing method for galvanized steel sheet |
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| CN109943837A (en) * | 2019-05-08 | 2019-06-28 | 兴化市华成镀锌管件有限公司 | A kind of surface treating agent for galvanized steel plain sheet |
| CN110616422B (en) * | 2019-10-08 | 2022-03-22 | 鞍钢股份有限公司 | Chromium-free environment-friendly passivator for galvanized sheet and preparation and use method thereof |
| CN111690920B (en) * | 2020-07-22 | 2022-02-08 | 武汉迪赛环保新材料股份有限公司 | Modified silica sol chromium-free passivator for surface treatment of hot-dip galvanized steel sheet and preparation method and application thereof |
| CN112959765A (en) * | 2021-04-06 | 2021-06-15 | 区绍贤 | Preparation process of plastic decorative sheet capable of purifying air for a long time |
| CN115233126A (en) * | 2022-08-05 | 2022-10-25 | 四川振鸿钢制品有限公司 | Steel surface galvanizing antiseptic treatment process |
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