AU2015361631B9 - Surface treating agent for hot-dip aluminum-zinc steel plate, and hot-dip aluminum-zinc steel plate and manufacturing method therefor - Google Patents
Surface treating agent for hot-dip aluminum-zinc steel plate, and hot-dip aluminum-zinc steel plate and manufacturing method therefor Download PDFInfo
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- AU2015361631B9 AU2015361631B9 AU2015361631A AU2015361631A AU2015361631B9 AU 2015361631 B9 AU2015361631 B9 AU 2015361631B9 AU 2015361631 A AU2015361631 A AU 2015361631A AU 2015361631 A AU2015361631 A AU 2015361631A AU 2015361631 B9 AU2015361631 B9 AU 2015361631B9
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 97
- 239000010959 steel Substances 0.000 title claims abstract description 97
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 61
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- FJMNNXLGOUYVHO-UHFFFAOYSA-N aluminum zinc Chemical compound [Al].[Zn] FJMNNXLGOUYVHO-UHFFFAOYSA-N 0.000 title abstract 3
- -1 carbodiimide compound Chemical class 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000000839 emulsion Substances 0.000 claims abstract description 18
- 238000005461 lubrication Methods 0.000 claims abstract description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 18
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 17
- 239000011737 fluorine Substances 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 15
- 150000003755 zirconium compounds Chemical class 0.000 claims abstract description 9
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 claims description 65
- 238000000576 coating method Methods 0.000 claims description 37
- 239000011248 coating agent Substances 0.000 claims description 36
- 239000002131 composite material Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 16
- 239000012802 nanoclay Substances 0.000 claims description 13
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 13
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- 239000000440 bentonite Substances 0.000 claims description 6
- 229910000278 bentonite Inorganic materials 0.000 claims description 6
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 6
- 150000001718 carbodiimides Chemical class 0.000 claims description 6
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- WRAGBEWQGHCDDU-UHFFFAOYSA-M C([O-])([O-])=O.[NH4+].[Zr+] Chemical compound C([O-])([O-])=O.[NH4+].[Zr+] WRAGBEWQGHCDDU-UHFFFAOYSA-M 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229920005906 polyester polyol Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 2
- 239000008119 colloidal silica Substances 0.000 claims description 2
- 239000007822 coupling agent Substances 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- 150000004760 silicates Chemical class 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 claims description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 2
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 25
- 230000007797 corrosion Effects 0.000 abstract description 25
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 150000003377 silicon compounds Chemical class 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 239000004927 clay Substances 0.000 abstract 1
- 235000015250 liver sausages Nutrition 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 16
- 238000011156 evaluation Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 230000008859 change Effects 0.000 description 9
- 229910052804 chromium Inorganic materials 0.000 description 9
- 239000011651 chromium Substances 0.000 description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 8
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 230000003247 decreasing effect Effects 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 229910000978 Pb alloy Inorganic materials 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 229910001430 chromium ion Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229910018137 Al-Zn Inorganic materials 0.000 description 1
- 229910018573 Al—Zn Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/12—Wash primers
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Coating With Molten Metal (AREA)
Abstract
A surface treating agent for a hot-dip aluminum-zinc steel plate. The surface treating agent has the following components in parts by mass: 45 to 85 parts of aqueous aliphatic polyurethane resin, 5 to 20 parts of an organic silicon compound, 3 to 15 parts of a carbodiimide compound emulsion; 1 to 5 parts, based on metallic elements, of a water soluble metal slat compound; 1 to 10 parts, based on zirconia, of a water soluble zirconium compound; 1 to 10 parts of water dispersive nanometer clay; and 1 to 15 parts of a fluorine-containing polymer lubrication additive. A steel pate coated with the surface treating agent has good corrosion resistance, tarnish resistance, and machinability.
Description
Surface treating agent for hot-plated aluminium-zinc steel plate, hot-plated aluminium-zinc steel plate and method for manufacturing the same
Technical field
The present invention relates to a surface treating agent for a steel plate, and particularly to a surface treating agent for a plated steel plate. The present invention also relates to a plated steel plate and a method for manufacturing the same.
Background Art
Since hot-plated aluminium-zinc steel plates have performance features, such as good corrosion resistance, a high heat reflectivity, heat resistance and an appearance decorative property, they are widely used in various fields of architectures, household appliances etc., for example, roofs and wall surfaces of lightweight steel structures, purlines, floor bearing plates, guardrails, sound barriers, drainage devices, etc., and also for example, large-scale electric appliance backplanes, electric appliance cabinet shells, household appliance chassis lamps, etc., in the household appliance industry. In particular, when a hot-plated aluminium-zinc steel plate is used as a household appliance outdoor piece, more strict requirements are proposed for the hot-plated aluminium-zinc steel plate due to rigorous outdoor service environment: for example, the surface of the steel plate is required to have excellent corrosion resistance to ensure that the steel plate is not corroded during the service of the steel plate; and also for example, the steel plate surface is required to have good stain resistance so as to prevent contaminants in the outdoor environment from easily adhering to the surface of the steel plate. Moreover, the hot-plated aluminium-zinc steel plate used for household appliance products further needs to undergo continuous punch formation, which also poses higher requirements for the processability of the steel. In addition, the surface of the hot-plated aluminium-zinc steel plate must also has a good lubricating property and abrasion resistance, i.e., it should be ensured, after the punching, that the surface of the steel plate cannot be blackened due to friction or furrowed such that good corrosion resistance can be provided for a relatively long period of time.
A Chinese patent document with a publication number of CN 1247777 A, published on 22 March 2000 and entitled “RESIN-COATED AL-ZN ALLOY COATED STEEL SHEET” discloses a resin-coated Al-Zn alloy coated steel sheet, which has good formation performance, anti-chromium solubility, corrosion resistance, alkali resistance and coatability, wherein a silane i
157972d-en coupling agent having amino groups, chromium ions, and an alcohol at least selected from one of C2-C3 trihydric alcohols and dihydric alcohols are incorporated into an emulsion of an acrylic polymer resin containing carboxyl groups and glycidyl groups and having an acid value of 10-60, and the resulting mixture is allowed to have a pH of 7-9 to obtain a chromium-containing resin composition. The chromium-containing resin composition is applied to a substrate so as to form an applied film, which is dried to obtain a resin film. The amount of the silane coupling agent is 0.5-3.0 wt.% of the resin solid component in the acrylic resin emulsion. The amount of the alcohol is 25-150 wt.% of the chromium ions (B). The amount of the resin film is 0.5-3.0 g/m2. The content of chromium ions (B) in the resin film is 5-50 mg/m2. The resin composition disclosed in the patent document is a chromium-containing product, which is not environmentally friendly and is not suitable for the household appliance industry.
A Chinese patent document with a publication number of CN 1530462 A, published on 22 September 2004, and entitled “METAL SURFACE PROCESSING AGENT AND STEEL PLATES WITH ALUMINIUM PLATED SUB-LEAD ALLOYS PROCESSED THEREBY” relates to a metal surface processing agent and steel plates with aluminium plated sub-lead alloys processed thereby, wherein the surface treating agent comprises: (A) an aqueous resin having combined carboxyl and acid amide; (B) one or more metal compounds selected from compounds of metals Al, Mg, Ca, Zn, Ni, Co, Fe, Zr, Ti, V, W, Mn and Ce; and (C) a surface treating agent for a metal material containing a silicon compound but not containing chromium; a steel plate plated with an alloy containing aluminium and sub-lead by a surface treatment with the above-mentioned treating agent is a steel plate with aluminium plated sub-lead alloy which has a coating layer containing the above-mentioned components (A), (B) and (C), and surface-treated with a single-face skin film adhesion amount of at least 0.2-5.0 g/m2 without containing chromium. The technical solution of the above-mentioned patent document does not involve the stain resistance and processability of a plated aluminium-zinc steel plate.
A Japanese patent document with a publication number of JP 2007-321224 A, published on 13 December 2007, and entitled “CHROMATE-FREE SURFACE-TREATED AL-ZN-BASED ALLOY-PLATED STEEL SHEET HAVING EXCELLENT CORROSION RESISTANCE AND ITS PRODUCTION METHOD” discloses a hot-plated aluminium-zinc steel plate having excellent corrosion resistance and water-resistant adherence, wherein the surface of the steel plate is covered with a chromium-free treated organic/inorganic composite protective film, and the protective film consisting of a silane-modified aqueous anion resin, a tetravalent vanadium compound and phosphoric acid or its compound, etc.
l I:\Interwoven\NRPortbl\DCC\AAR\l 9760259_ 1 .docx-16/01/2020
2015361631 16 Jan 2020
Summary of the Invention
The present invention seeks to provide a surface treating agent for a hot-plated aluminium-zinc steel plate, and a steel plate coated with the surface treating agent has excellent corrosion resistance, superior stain resistance and good processability. In addition, the surface treating agent of the present invention does not contain chromium and has good stability, and provides better environmentally friendly and economic benefits.
The present invention provides a surface treating agent for a hot-plated aluminium-zinc steel plate, the part by mass of each components thereof are as follows:
an aqueous aliphatic polyurethane resin: 45-85 parts by mass;
an organosilicon compound: 5-20 parts by mass;
a carbodiimide compound emulsion: 3-15 parts by mass;
a water soluble metal salt compound, in part by mass by the metal element: 1-5 parts by mass;
a water soluble zirconium compound, in part by mass by zirconia: 1-10 parts by mass;
a water-dispersed nano clay: 1-10 parts by mass; and a fluorine-containing polymer lubrication auxiliary: 1-15 parts by mass.
In the above-mentioned technical solution, the aqueous aliphatic polyurethane resin is a polyester polyol-based aliphatic anionic aqueous polyurethane resin, which may be an aqueous solution or may also be water-dispersed, and has a solid content of 30-40%. When the part by mass of the aqueous aliphatic polyurethane resin is lower than 45 parts, both the weather resistance and corrosion resistance of the coating will be decreased; and when the part by mass of the component exceeds 85 parts, the alkali resistance of the coating will become poor. Preferably, the part by mass of the aqueous aliphatic polyurethane resin is controlled at 55-70 parts.
In this technical solution, the reason why the part by mass of the organosilicon compound is set as 5-20 parts lies in: if the part by mass of the organosilicon compound is less than 5 parts, the adhesion and corrosion resistance of the coating will be decreased; and if the part by mass of the organosilicon compound is greater than 20 parts, the corrosion resistance of the coating will be decreased, and the stability of the surface treating agent will also become poor. Further, the part by mass of the organosilicon compound can also be set as 7-15 parts.
In the technical solution of the present invention, the carbodiimide compound emulsion can be reacted with carboxyl groups in the aqueous aliphatic polyurethane resin so as to improve the crosslinking degree of the composite coating. If the part by mass of the carbodiimide compound
157972d-en emulsion on the aqueous aliphatic polyurethane resin will not be obvious, and the insufficiency of cross-linking degree of the coating will result in a decrease of corrosion resistance; and if the part by mass of the carbodiimide compound emulsion is higher than 15 parts, the reaction between the carbodiimide compound emulsion and aqueous aliphatic polyurethane resin is excessively violently, which tends to a gel phenomenon, thus leading to a decrease of stability of the surface treating agent. In order to obtain a better technical effect, the part by mass of the carbodiimide compound emulsion can be further controlled at 4-10 parts.
It is necessary to state herein that the solid content of carbodiimide in the above-mentioned carbodiimide compound emulsion is 35-50% and the equivalent of carbodiimide is 380-590.
Furthermore, with regard to the water soluble metal salt compound, the part by mass by the metal elements contained is 1 -5 parts. When the part by mass of the total amount of metal elements present in the water soluble metal salt compound is lower than 1 part, the under-film corrosion expansion resistance of the coating is poorer; and when the part by mass of the total amount of metal elements present in the water soluble metal salt compound is higher than 5 parts, the metal ions affect the stability of the surface treating agent, leading to a d ecrease in stability of the surface treating agent. Preferably, the part by mass of the water soluble metal salt compound is designed to be 2-4 parts.
On the basis of the technical solution of the present invention, the water soluble zirconium compound is added according to the part by mass of zirconia. If the part by mass by zirconia is less than 1 part, both the ultraviolet ageing resistance and adhesion of the coating will be poorer; and if the part by mass by zirconia is less than 10 parts, the stability of the surface treating agent is decreased. Preferably, the part by mass of the water soluble zirconium compound is designed to be 3-6 parts.
In the present invention, the part by mass of the water-dispersed nano clay in the surface treating agent is designed to be 1-10 pails, because: if the part by mass of the water-dispersed nano clay does not reach 1 part, this results in the decrease of the corrosion resistance and stain resistance of the coating; and if the part by mass of the water-dispersed nano clay exceeds 10 parts, the viscosity of the surface treating agent will be substantially increased, which in turn results in the decrease of the application property and stability of the surface treating agent. Preferably, the part by mass of the water-dispersed nano clay can be designed to be 2-6 parts.
In the technical solution of the present invention, the part by mass of the fluorine-containing polymer lubrication auxiliary is controlled at 1-15 parts, the reason being: when the part by mass of the fluorine-containing polymer lubrication auxiliary is less than 1 part, the lubricating property of the coating is insufficient; and when the part by mass of the
157972d-en fluorine-containing polymer lubrication auxiliary is greater than 15 parts, both the corrosion resistance and weather resistance of the coating may be decreased. As a more preferred setting range, the part by mass of the fluorine-containing polymer lubrication auxiliary is controlled at
3-10 parts.
Further, in the surface treating agent for a hot-plated aluminium-zinc steel plate of the present invention, the above-mentioned organosilicon compound is at least one of silicic acid, silicates, colloidal silica and organic silane coupling agents.
More further, in the surface treating agent for a hot-plated aluminium-zinc steel plate of the present invention, the above-mentioned organosilicon compound is an organic silane coupling agent, which is at least one of vinyl silane coupling agents, epoxy silane coupling agents and mercapto silane coupling agents.
Further, in the surface treating agent for a hot-plated aluminium-zinc steel plate of the present invention, the above-mentioned water soluble zirconium compound is ammonium zirconium carbonate.
Further, in the surface treating agent for a hot-plated aluminium-zinc steel plate of the present invention, the above-mentioned water-dispersed nano clay is at least one of nano montmorillonite, nano bentonite and polyphosphate-modified nano bentonite.
Taking the polyphosphate-modified nano bentonite as an example, it can be uniformly spread in the coating as a nano lamella layer to significantly improve the corrosion resistance and stain resistance of the coating.
Further, in the surface treating agent for a hot-plated aluminium-zinc steel plate of the present invention, the above-mentioned fluorine-containing polymer lubrication auxiliary is a polytetrafluoroethylene wax and/or polyfluo wax.
Further, in the surface treating agent for a hot-plated aluminium-zinc steel plate of the present invention, the average particle diameter of the above-mentioned fluorine-containing polymer lubrication auxiliary is 0.1-2.0 microns.
The inventor has found that when the average particle diameter of the fluorine-containing polymer lubrication auxiliary is lower than 0.1 microns or higher than 2.0 microns, the processability of the composite coating will be decreased in both cases. Therefore, in order to improve the processability of the steel plate coated with the composite coating, it is preferred to define the average particle diameter of the fluorine-containing polymer lubrication auxiliary in a range between 0.1-2.0 microns; and more preferably, the average particle diameter of the fluorine-containing polymer lubrication auxiliary can also be controlled between 0.3-1.0 micron.
Another object of the present invention is providing a hot-plated aluminium-zinc steel plate,
157972d-en which has excellent corrosion resistance, superior surface stain resistance and good processability. In addition, the hot-plated aluminium-zinc steel plate coated with the surface treating agent does not contain the harmful element chromium in the surface, is an environmentally friendly product, and can be used in the relevant industry fields of building, household appliances, etc.
In order to achieve the above-mentioned object, the present invention provides a hot-plated aluminium-zinc steel plate, of which the surface has a composite coating coated by any surface treating agent as mentioned above.
Further, the composite coating of the hot-plated aluminium-zinc steel plate of the present invention has a dry film thickness of 1-3 microns.
If the dry film thickness of the composite coating does not reach 1 micron, the composite coating applied on the surface of the steel plate will be thinner, thus leading to a decrease of comprehensive properties of the steel plate, such as punching processability, corrosion resistance, stain resistance.
Accordingly, the present invention also discloses a method for manufacturing the above hot-plated aluminium-zinc steel plate, which comprises: applying the surface treating agent on at least one surface of the hot-plated aluminium-zinc steel plate, and drying at 80-180°C, to obtain a hot-plated aluminium-zinc steel plate having a composite coating on the surface.
The hot-plated aluminium-zinc steel plate is obtained by the above-mentioned manufacturing method, by means of one pass coating on the surface of the steel plate, and after the completion of the coating, drying at between 80-180°C to obtain a hot-plated aluminium-zinc steel plate having a composite coating on the surface. If the temperature is lower than 80°C, the cross-linking of the composite coating is not sufficient, leading to a decrease of their various properties; and if the temperature is higher than 180°C, the properties of some components in the surface treating agent will change, thus affecting the final effect of the composite coating applied on the steel plate.
In the above-mentioned technical solution, the composite coating may be directly applied on the surface of the hot-plated aluminium-zinc steel plate by roller coating or spray coating.
With regard to the above-mentioned technical solution, the above-mentioned composite coating may be applied on merely one side of the hot-plated aluminium-zinc steel plate, or both sides of the hot-plated aluminium-zinc steel plate.
The heating and drying method for the composite coating in the method for manufacturing the hot-plated aluminium-zinc steel plate of the present invention is not particularly limited, and heating methods such as hot blast heating, induction heating, infrared heating may be used.
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After coating the surface of the steel plate with the surface treating agent for a hot-plated aluminium-zinc steel plate of the present invention, the steel plate has excellent corrosion resistance, superior stain resistance, good processability and better weather resistance.
In addition, the surface treating agent of the present invention does not contain chromium and has good system stability, and provides better environmentally friendly and economic benefits.
After the hot-plated aluminium-zinc steel plate of the present invention is coated with the surface treating agent, good comprehensive performances such as corrosion resistance, stain resistance, weather resistance, and processability are provided.
By the method for manufacturing a hot-plated aluminium-zinc steel plate of the present invention, a hot-plated aluminium-zinc steel plate having excellent corrosion resistance, superior surface stain resistance, better weather resistance and good processability can be obtained.
Particular Embodiments
The surface treating agent for a hot-plated aluminium-zinc steel plate, hot-plated aluminium-zinc steel plate and the method for manufacturing the same, as described in the present invention will be further explained and illustrated below in combination with particular Examples; however, the explanation and description do not form an inappropriate definition of the technical solutions of the present invention.
Examples 1-7 and Comparative Examples 1-3
In each of Examples 1-7 and Comparative Examples 1-3, a hot-plated aluminium-zinc steel plate having a plate thickness of 1.0 mm is used, a surface treating agent (the part by masses of various components of the surface treating agent being as shown in table 1 in detail) is applied on at least one surface of the hot-plated aluminium-zinc steel plate, and after drying at 80-180°C, a hot-plated aluminium-zinc steel plate having a composite coating on the surface is obtained, the dry film thickness of the composite coating being 1 -3 microns, specific parameters of the drying process being as shown in table 2 in detail.
Table 1 lists the part by masses of various components of composite coatings in Examples 1-7 and Comparative Examples 1-3.
Table 1.
| Number | Exampl e 1 | Examp le2 | Examp le 3 | Examp le 4 | Examp le 5 | Examp le 6 | Examp le 7 | Comparati ve Example 1 | Comparati ve Example 2 | Comparati ve Example 3 |
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| aqueous aliphatic polyurethane resin (A) | Type* | A | A | A | A | A | A | A | A | A | A |
| part by mass | 75 | 65 | 70 | 67 | 70 | 60 | 65 | 65 | 70 | 75 | |
| Organosilico n compound (B) | Type* | Bl | B2 | B3 | Bl | B2 | B3 | B2 | Bl | B2 | B3 |
| part by mass | 10 | 13 | 11 | 9 | 8 | 10 | 15 | 15 | 13 | 11.5 | |
| Carbodiimide compound emulsion (C) | Type* | c | c | C | C | C | c | C | - | C | C |
| part by mass | 4.0 | 3.5 | 4.0 | 10 | 4.0 | 8.0 | 5.0 | - | 3.0 | 4.0 | |
| Water soluble metal salt compound (D) | Type* | DI | DI | DI | DI | D2 | D2 | D2 | DI | D2 | DI |
| part by mass (by metal element) | 2.0 | 3.0 | 1.0 | 1.0 | 2.0 | 3.0 | 4.0 | 5.0 | 3.0 | 3.0 | |
| Water soluble zirconium compound (E) | Type* | E | E | E | E | E | E | E | E | E | E |
| part by mass (by zirconia) | 2.0 | 3.0 | 2.0 | 2.0 | 4.0 | 6.0 | 5.0 | 5.0 | 6.0 | 4.0 | |
| water-dispers ed nano clay (F) | Type* | Fl | Fl | Fl | Fl | F2 | F2 | F3 | F3 | - | F3 |
| part by mass | 2.0 | 5.5 | 2.0 | 1.0 | 5.0 | 6.0 | 2.0 | 3.0 | - | 2.5 | |
| Fluorine-cont aining polymer lubrication auxiliary (G) | Type* | G1 | G1 | G1 | G1 | G2 | G2 | G2 | G1 | G2 | - |
| part by mass | 3.0 | 7.0 | 10 | 3.0 | 7.0 | 4.0 | 4.0 | 7.0 | 5.0 | - |
*NOTE: A is an aqueous aliphatic polyurethane resin; Bl is vinyl trimethoxy silane, B2 is
157972d-en epoxypropyloxypropyl trimethoxy silane, and B3 is aminopropyl triethoxy silane; C is a carbodiimide compound emulsion; DI is vanadium oxide, and D2 is ammonium fluorotitanate; E is ammonium zirconium carbonate; Fl is polyphosphate-modified nano montmorillonite, F2 is nano bentonite, and F3 is nano montmorillonite; and G1 is a polytetrafluoroethylene wax, and G2 is a polyfluo wax.
Table 2 lists parameters of the drying process in the method for manufacturing the hot-plated aluminium-zinc steel plate in Examples 1-7 and Comparative Examples 1-3.
Table 2.
| Number | Drying temperature (°C) |
| Example 1 | 100 |
| Example 2 | 90 |
| Example 3 | 120 |
| Example 4 | 130 |
| Example 5 | 110 |
| Example 6 | 140 |
| Example 7 | 150 |
| Comparative Example 1 | 80 |
| Comparative Example 2 | 120 |
| Comparative Example 3 | 120 |
The hot-plated aluminium-zinc steel plates coated with the surface treating agents in the above-mentioned Examples 1-7 and Comparative Examples 1-3 are sampled and then tested according to the following test methods, and then the obtained test data for evaluation of various properties are listed in table 3. In these methods, the tests of various performance parameters are as follows:
1) Corrosion resistance
A brine spray test is performed on a test sample plate (a flat plate), with the test standard being ASTM Bl 17 and the test time being 240 hours, evaluation criteria being as follows:
O: the white rust area rate is less than or equal to 5%;
o: the white rust area rate is greater than 5% and less than or equal to 10%;
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Δ: the white rust area rate is greater than 10% and less than or equal to 50%; and x: the white rust area rate is greater than 50%.
2) Stain resistance
A 5% carbon black suspension is dropwise added on the surface of a test sample plate to allow same to form an approximately round water stain having a diameter of about 50 mm, the test sample plate is taken out after baking at 60°C for 1 h, and blown to dryness after the residual carbon black on the surface has been washed off, and the changes of before-after colour difference (ΔΕ*) in the water stain area is measured, the evaluation criteria being as follows:
©: the colour difference ΔΕ* is less than or equal to 3.0, the surface stain resistance being excellent;
o; the colour difference ΔΕ* is greater than 3.0 and less than or equal to 6.0;
Δ: the colour difference ΔΕ* is greater than 6.0 and less than or equal to 9.0; and x; the colour difference ΔΕ* is greater than 9.0, the surface contamination is serious.
3) Processability
3a. After a test sample plate is subjected to a T bend test, the peeling degree of the skin film after processing is evaluated using a tape stripping method, the evaluation criteria being as follows:
©: no peeling-off occurs to the skin film at 2T;
o: no peeling-off occurs to the skin film at 3T;
Δ: no peeling-off occurs to the skin film at 4T; and x: no peeling-off occurs to the skin film at 5T.
3b. A brake bead method is used for the test, under experimental conditions where the pressure under bead is fixed at 3 KN, the pressure head diameter is 9.6 mm, and the drawing speed is 200 mm/min. The appearance was observed after drawing, the evaluation criteria being as follows:
©: the appearance has no change;
o; a small amount of black points on the appearance;
Δ: relatively more obvious black stripes on the appearance;
x: the overall appearance becomes black.
4) Weather resistance
A sample plate is placed in an ultraviolet ageing test box (a UVB-313 lamp tube), having 8
157972d-en h as a cycle period, with ultraviolet light illumination of 4 h at a black panel temperature of 60 ± 3°C, and condensation of 4 h at a black panel temperature of 50 ± 3°C, and after 600 h, the appearance of the sample plate was observed and the gloss retention rate was measured, the evaluation criteria being as follows:
O: the appearance of the sample plate has no obvious change, the gloss retention being greater than or equal to 70%;
o: the appearance of the sample plate has a slight change, the gloss retention being greater than or equal to 50% and less than 70%;
Δ: the appearance of the sample plate has a remarkable change, the gloss retention being greater than or equal to 30% and less than 50%; and x: the appearance of the sample plate has a serious change, the gloss retention being less than 30%.
5) Storage stability
The surface treating agent is placed at room temperature, and the change of the solution is observed after 90 days, the evaluation criteria being as follows:
©: no change;
o: slightly thickened (functioning normally);
Δ: seriously thickened; and x: gel.
Table 3 lists various performance parameters of the hot-plated aluminium-zinc steel plates coated with the surface treating agents in Examples 1-7 and Comparative Examples 1-3.
Table 3.
| Number | Various performance parameters | |||||
| Corrosion resistance | Stain resistance | Weather resistanc e | Processability | Storage stability | ||
| T bend | Drawing | |||||
| Example 1 | © | o | © | © | © | © |
| Example 2 | © | © | o | © | © | © |
| Example 3 | © | © | o | © | © | © |
| Example 4 | o | o | © | 0 | o | © |
| Example 5 | o | © | o | © | © | © |
| Example 6 | © | © | © | 0 | o | o |
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| Example 7 | © | © | © | 0 | o | © |
| Comparative Example 1 | Δ | X | X | 0 | o | o |
| Comparative Example 2 | O | X | o | 0 | o | Δ |
| Comparative Example 3 | o | Δ | o | X | X | V,·1 |
As can be seen in combination of Table 1 and Table 3, since in Comparative Example 1, no carbodiimide compound emulsion (C) is contained, the cross-linking degree of the composite coating is insufficient, thus leading to poorer stain resistance, corrosion resistance and weather resistance (the evaluation results being “Δ” or “x”); since no water-dispersed nano clay (F) is added in Comparative Example 2, the stain resistance of the composite coating is poorer (the evaluation results being “x”); and since no fluorine-containing polymer lubrication auxiliary (G) is added in Comparative Example 3, the processability of the steel plate is poorer (the evaluation result being “x”).
As can be seen from table 3, as compared to Comparative Examples 1-3, after the hot-plated aluminium-zinc steel plates in Examples 1-7 are subjected to the above-mentioned various tests, the evaluation results are all “©” and “o”, which indicates that the hot-plated aluminium-zinc steel plates coated with the surface treating agent of the present invention all show excellent corrosion resistance, superior stain resistance, better weather resistance and good processability. In addition, it can be seen that with regal'd to the stabilities of storage of the hot-plated aluminium-zinc steel plates in Examples 1-7, no property change easily occurs after a longer time of storage, such that the effect of the surface treating agent on the comprehensive performance of the hot-plated aluminium-zinc steel plates can be avoided as far as possible.
It should be noted that those listed above are merely particular embodiments of the present invention, and obviously, the present invention is not limited to the above embodiments, and can have many similar changes. With regard to all variants, if directly derived or conceived from the contents disclosed in the present invention by a person skilled in the art, they shall all fall within the scope of protection of the present invention.
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2015361631 16 Jan 2020
Throughout this specification, unless the context requires otherwise, the word comprise or variations such as comprises or comprising, will be understood to imply the inclusion of a stated element or integer or method step or group of elements or integers or method steps but not the exclusion of any element or integer or method step or group of elements or integers or method steps.
The reference in this specification to any prior publication (or information derived from it), or to any matter which is known, is not, and should not be taken as an acknowledgement or admission or any form of suggestion that the prior publication (or information derived from it) or known matter forms part of the common general knowledge in the field of endeavour to which this specification relates.
Claims (17)
1. A surface treating agent for a hot-plated aluminium-zinc steel plate, consisting of: an aqueous aliphatic polyurethane resin: 45-85 parts by mass;
an organosilicon compound: 5-20 parts by mass;
a carbodiimide compound emulsion: 3-15 parts by mass;
a water soluble metal salt compound, in part by mass by the metal element: 1-5 parts by mass;
a water soluble zirconium compound, in part by mass by zirconia: 1-10 parts by mass;
a water-dispersed nano clay: 1-10 parts by mass; and a fluorine-containing polymer lubrication auxiliary: 1-15 parts by mass.
2. The surface treating agent for a hot-plated aluminium-zinc steel plate of claim 1, wherein:
the amount of the aqueous aliphatic polyurethane resin is 65-75 parts by mass;
the amount of the organosilicon compound is 7-15 parts by mass;
the amount of the carbodiimide compound emulsion is 3-10 parts by mass;
the amount of the water-dispersed nano clay is 2-6 parts by mass; and the amount of the fluorine-containing polymer lubrication auxiliary is 3-10 parts by mass.
3. The surface treating agent for a hot-plated aluminium-zinc steel plate of claim 1 or 2, wherein the aqueous aliphatic polyurethane resin is a polyester polyol-based aliphatic anionic aqueous polyurethane resin, which is an aqueous solution or is water-dispersed, and has a solid content of 30-40%.
4. The surface treating agent for a hot-plated aluminium-zinc steel plate of any one of claims 1 to 3, wherein said organosilicon compound is at least one of silicic acid, silicates, colloidal silica and organic silane coupling agents.
5. The surface treating agent for a hot-plated aluminium-zinc steel plate of claim 4, wherein said organosilicon compound is an organic silane coupling agent, which is at least l I:\Interwoven\NRPortbl\DCC\AAR\l 9760259_ I .docx-16/01/2020
2015361631 16 Jan 2020 one of vinyl silane coupling agents, epoxy silane coupling agents and mercaptosilane coupling agents.
6. The surface treating agent for a hot-plated aluminium-zinc steel plate of claim 4, wherein said organosilicon compound is vinyl trimethoxy silane, epoxypropyloxypropyl trimethoxy silane or aminopropyl triethoxy silane.
7. The surface treating agent for a hot-plated aluminium-zinc steel plate of any one of claims 1 to 6, wherein said water soluble zirconium compound is ammonium zirconium carbonate.
8. The surface treating agent for a hot-plated aluminium-zinc steel plate of any one of claims 1 to 7, wherein said water-dispersed nano clay is at least one of nano montmorillonite, nano bentonite and polyphosphate-modified nano bentonite.
9. The surface treating agent for a hot-plated aluminium-zinc steel plate of any one of claims 1 to 8, wherein said water-dispersed nano clay is polyphosphate-modified nano montmorillonite.
10. The surface treating agent for a hot-plated aluminium-zinc steel plate of any one of claims 1 to 9, wherein said fluorine-containing polymer lubrication auxiliary is a polytetrafluoroethylene wax and/or polyfluo wax.
11. The surface treating agent for a hot-plated aluminium-zinc steel plate of any one of claims 1 to 10, wherein the average particle diameter of said fluorine-containing polymer lubrication auxiliary is 0.1-2.0 microns.
12. The surface treating agent for a hot-plated aluminium-zinc steel plate of any one of claims 1 to 11, wherein the solid content of carbodiimide in the carbodiimide compound emulsion is 35-50% and the equivalent of carbodiimide is 380-590.
13. The surface treating agent for a hot-plated aluminium-zinc steel plate of any one of claims 1 to 12, wherein the water soluble metal salt compound is vanadium oxide.
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2015361631 16 Jan 2020
14. The surface treating agent for a hot-plated aluminium-zinc steel plate of any one of claims 1 to 13, wherein:
the amount of the aqueous aliphatic polyurethane resin is 55-75 parts by mass;
the amount of the organosilicon compound is 10-15 parts by mass;
the amount of the carbodiimide compound emulsion is 4-8 parts by mass;
the amount of the water soluble metal salt compound, in part by mass by the metal element, is 1-5 parts by mass;
the amount of the water soluble zirconium compound, in part by mass by zirconia, is 2-6 parts by mass;
the amount of the water-dispersed nano clay is 2-6 parts by mass; and the amount of the fluorine-containing polymer lubrication auxiliary is 3-10 parts by mass;
wherein the aqueous aliphatic polyurethane resin is a polyester polyol-based aliphatic anionic aqueous polyurethane resin, which is an aqueous solution or is waterdispersed, and has a solid content of 30-40%; and the solid content of carbodiimide in the carbodiimide compound emulsion is 35-50% and the equivalent of carbodiimide is 380590.
15. A hot-plated aluminium-zinc steel plate, of which the surface has a composite coating coated with the surface treating agent of any one of claims 1 to 14.
16. The hot-plated aluminium-zinc steel plate of claim 15, wherein said composite coating has a dry film thickness of 1-3 microns.
17. A method for manufacturing the hot-plated aluminium-zinc steel plate of claim 15, characterized by applying the surface treating agent on at least one surface of the hotplated aluminium-zinc steel plate, and drying at 80-180°C, to obtain a hot-plated aluminium-zinc steel plate having a composite coating on the surface.
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| CN201410766495.9A CN105733430A (en) | 2014-12-11 | 2014-12-11 | Surface treatment agent for hot-dip Al-Zn coated steel sheet, the hot-dip Al-Zn coated steel sheet and production method thereof |
| PCT/CN2015/095361 WO2016091059A1 (en) | 2014-12-11 | 2015-11-24 | Surface treating agent for hot-dip aluminum-zinc steel plate, and hot-dip aluminum-zinc steel plate and manufacturing method therefor |
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| US11214692B2 (en) | 2017-12-04 | 2022-01-04 | Hamilton Sundstrand Corporation | Increasing anti-corrosion through nanocomposite materials |
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| CN113527991B (en) * | 2020-04-16 | 2022-06-24 | 宝山钢铁股份有限公司 | Environment-friendly water-based surface treating agent for color-coated substrate and using method thereof |
| CN113522706B (en) * | 2020-04-16 | 2022-10-21 | 宝山钢铁股份有限公司 | Surface treatment color coating substrate suitable for radiation curing type color plate production process |
| CN114075663B (en) * | 2020-08-21 | 2023-09-12 | 宝山钢铁股份有限公司 | Water-based treating agent for carbon steel surface, well corrosion-resistant carbon steel and preparation method thereof |
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