CN102504700A - Aqueous chromium-free zinc and aluminum coating and preparation method thereof - Google Patents
Aqueous chromium-free zinc and aluminum coating and preparation method thereof Download PDFInfo
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- CN102504700A CN102504700A CN2011103521670A CN201110352167A CN102504700A CN 102504700 A CN102504700 A CN 102504700A CN 2011103521670 A CN2011103521670 A CN 2011103521670A CN 201110352167 A CN201110352167 A CN 201110352167A CN 102504700 A CN102504700 A CN 102504700A
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- 238000000576 coating method Methods 0.000 title claims abstract description 77
- 239000011248 coating agent Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 title abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title abstract description 5
- 229910052725 zinc Inorganic materials 0.000 title abstract description 5
- 239000011701 zinc Substances 0.000 title abstract description 5
- 229910000611 Zinc aluminium Inorganic materials 0.000 claims abstract description 52
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 50
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- -1 ion compounds Chemical class 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 239000002562 thickening agent Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 16
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 13
- 150000007942 carboxylates Chemical class 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 11
- 230000008719 thickening Effects 0.000 claims description 10
- 239000006071 cream Substances 0.000 claims description 7
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 7
- 239000003921 oil Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 239000002480 mineral oil Substances 0.000 claims description 4
- 235000010446 mineral oil Nutrition 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 4
- 229920002635 polyurethane Polymers 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- 150000002632 lipids Chemical class 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 9
- 239000003960 organic solvent Substances 0.000 abstract description 5
- 229910052793 cadmium Inorganic materials 0.000 abstract description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract description 3
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052753 mercury Inorganic materials 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract 2
- 231100000331 toxic Toxicity 0.000 abstract 1
- 230000002588 toxic effect Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 14
- 239000002390 adhesive tape Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 238000001723 curing Methods 0.000 description 12
- 239000007921 spray Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 5
- 238000009736 wetting Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 238000005422 blasting Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- BULVZWIRKLYCBC-UHFFFAOYSA-N phorate Chemical compound CCOP(=S)(OCC)SCSCC BULVZWIRKLYCBC-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 229910001037 White iron Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000000873 masking effect Effects 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052909 inorganic silicate 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
- 238000005065 mining Methods 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses aqueous chromium-free zinc and aluminum coating. The coating comprises an agent A and an agent B, which are mixed and blended uniformly when the coating is used, wherein based on the total weight, which is 100 percent, of the agent A and the agent B, the agent A comprises 1 to 5 weight percent of emulsifier, 10 to 25 weight percent of ethanol, 0 to 5 weight percent of deforming agent, 0 to 0.3 weight percent of thickener and 25 to 35 weight percent of metal zinc aluminum powder or zinc aluminum paste; and the agent B comprises 20 to 40 weight percent of deionized water, and 10 to 20 weight percent of silane coupling agent. The aqueous chromium-free zinc and aluminum coating does not contain hexavalent chromium, lead, mercury and cadmium heavy metal ion compounds or toxic organic solvents such as benzene and dimethylbenzene. The curing temperature of the coating is 250 to 300 DEG C, and the curing time of the coating is 20 minutes which is much shorter. The invention also provides the preparation method and the coating method of the aqueous chromium-free zinc and aluminum coating.
Description
Technical field
Technical scheme of the present invention relates to a kind of water-borne coatings and preparation method thereof, is specifically related to a kind of aqueous chromium-free zinc-aluminium coating and preparation method thereof.
Background technology
Market now; The etch-proof DACROMET paint spraying of ferrous metal product technology is replaced by chromium-free zinc aluminum coating GEOMET, DEITAMKS, MAGNi, ZiNTEK a few days ago, is main product with water-based, Chrome-free, environmentally friendly GEOMET especially wherein.GEOMET coating does not contain any resinous principle; This can provide the water-dilutable based coating composition of corrosionproof protection at document CN1172135A; Disclosed a kind of in water medium; With the epoxy of silane coupling agent and the hydroxyl of silanol functional group and nonylphenol Soxylat A 25-7; (355 ℃) condensations (crosslinked) generate low molecular organosilicon hydrocarbon chain compound as tackiness agent (film forming matter) under hot conditions, and filler aggregate-fine zinc-aluminium plate, finally process iron-based ground protective system.
But proof is produced in industriallization application in the past few years; This coating has the unpleasant people's of choking organic solvent taste; The necessity that this harmful unpleasant organic solvent exists is to have in the coating material composition of harmless usual vehicle indissoluble, and this coating is short work-ing life, only just loses efficacy in 30 days.
In addition, disclosed coating in the CN1172135A patented claim needs 355 ℃ of storing temperatures, and not only consumes energy is too high, also so high bake for spring-like, female type of high-strength bolt, sheet type workpiece is prone to cause annealing and thermal distortion accident.And contain a large amount of microvesicles in the coating, general coating is inoperative fully with froth breaking or suds suppressor, finally directly influences the quality and the outward appearance of application product.
Summary of the invention
In order to solve the problem that exists in the prior art; The present invention provides a kind of aqueous chromium-free zinc-aluminium coating; Said aqueous chromium-free zinc-aluminium coating comprises and mixes the A agent and the B agent of mixing well when using, and is 100% with the total weight of said A agent and B agent, and said A agent comprises following components in weight percentage:
Emulsifying agent: 1%-5%,
Alcohol: 10%-25%,
Skimmer: 0%-5%,
Thickening material: 0%-0.3%,
Metallic zinc aluminium powder or zinc-aluminium cream: 25%-35%;
Said B agent comprises following components in weight percentage:
Deionized water: 20%-40%,
Silane coupling agent: 10%-20%;
Wherein, said emulsifying agent is selected from one or more in AEO, polyoxyethylene carboxylate, the polyoxyethylene polyoxypropylene block polyether;
Said alcohol is selected from 1, ammediol, dipropylene glycol or their mixture;
Said skimmer is selected from mineral oil origin water-based skimmer or solvent oil; Said mineral oil origin water-based skimmer preferably adopts the BNK-G303 skimmer, and said solvent oil preferably adopts the 200# solvent oil.
Said thickening material is selected from one or several in Natvosol, Vltra tears, the nonionic polyurethane associative thickener;
The mass ratio of the zinc-aluminium in said metallic zinc aluminium powder or the zinc-aluminium cream is: 3:1-7:1 is preferably 3:1-5:1;
Said silane coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane.
Preferably, said metallic zinc aluminium powder is a sheet, and thickness is 0.1-0.3 μ m, and particle diameter is 8-15 μ m, and loose density is 0.9-1.2g/cm
3
Preferably, zinc-aluminium content is 85wt%～96wt%, more preferably 89wt%～95wt% in the said zinc-aluminium cream.
Preferably, said alcohol is 1, the mixture of ammediol and dipropylene glycol, and 1, the weight ratio of ammediol and dipropylene glycol is 4:6.
Preferably; Said emulsifying agent is the mixture of AEO and polyoxyethylene carboxylate; And the weight ratio of AEO and polyoxyethylene carboxylate is 3/7-1, and the HLB value of the mixture of said AEO and said polyoxyethylene carboxylate is 12-15.Preferred, Fatty Alcohol(C12-C14 and C12-C18) is C in the said AEO
14～22Synthol, wherein, the polyoxyethylated polymerization degree is 4-20; Lipid acid is C in the said polyoxyethylene carboxylate
16～22Sfas, wherein, the polyoxyethylated polymerization degree is 7-20.
The preparation method of aqueous chromium-free zinc-aluminium coating of the present invention may further comprise the steps:
Preparing A agent step: said emulsifying agent, alcohol, skimmer, metallic zinc aluminium powder or zinc-aluminium cream are mixed, be uniformly dispersed, add thickening material again, stir with stirrer;
Preparation B agent step: said silane coupling agent is added in the deionized water, be stirred to said solution and be till the water white transparency;
Mixing step: said A agent is added in the said B agent, stir water-based zinc-aluminium coating.
Preferably, in the said preparing A agent step, adopt high speed dispersor during dispersion, disperseing rotating speed is 1400 rev/mins, and said mixing speed is 600～800 rev/mins.
Beneficial effect of the present invention is following:
1. aqueous chromium-free zinc-aluminium coating non-hexavalent chromium of the present invention and lead, mercury, cadmium heavy metal ion compound do not contain poisonous organic solvents such as benzene, YLENE, and the coating curing temperature is 250-300 ℃, gets final product in 20 minutes, has shortened the time widely.
2. use this preparation method to realize the environmental friendliness of coating material production, energy-saving and emission-reduction have ensured that operator produce and personnel safety, have accomplished the work situation hygiene.Coating of the present invention had detected through international logical mark SGS already and had identified, met the code requirement of 2000/53/EG of European Union and ROHS instruction fully.
Embodiment
The present invention will be described below in conjunction with embodiment:
Effect testing method
1. the preparation of test sample plate
Adopt the cold-rolling mild steel plate of 150 * 70 * 1.0mm, at one end make a call to a Φ 6mm hole, standard jig is immersed in earlier in the 200# solvent oil before coating and cleans greasy dirt with hairbrush, airing.Subsequently, frustrate four limits with file, to put into moisture eliminator after greyish white iron-based (activation) covers with soft paper bag subsequent use to exposing to use the artificial polishing of 0# sand paper (cloth) again.
2. the pre-treatment of test iron-based component
M12～18 screw rods are some; Or own component of machine is some; With alkaline cleaner aqueous solution soaking (70 ℃ of temperature) deoiling, after the drying, send into track type shot-blasting machine shot blasting earlier; The shot-blasting machine shot is Φ 0.2～0.3mm, and it is qualified that ball blast exposed greyish white iron-based to workpiece in 15～30 minutes.After getting half the above-listed component and doing bonderizing, it is subsequent use to put into moisture eliminator.Be chilled to room temperature behind second half component ball blast, wrap up in soft paper bag that to put into moisture eliminator subsequent use.
3. adhesion test
Adopt the 3N/cm of Minnesota Mining and Manufacturing Company
2Adhesive tape (sign special adhesive tape) detects coating adhesion, and operative norm GB/T5270-2005-stroke lattice adhesive tape method one-level is qualified.
4. neutral salt spray test (NSS)
Carrying out GB GB/T 10125-1997, is the termination test hours a red rust point to occur.
Embodiment 1
1. preparing A agent
By ratio of weight and the number of copies; Get 17.5 part 1; Ammediol, 1 part of AEO (homemade trade mark O-10), 1.4 parts of AEOs (homemade trade mark A-20), 3 parts of 200# solvent oils, 2 parts of polyoxyethylene polyoxypropylene block polyethers (homemade trade mark X-1005); Mix and stir, add 25 parts of sheet composite powders that the zinc-aluminium weight ratio is 5:1, with abundant wetting being uniformly dispersed of Ke Lesi high speed dispersor (1400 rev/mins of rotating speeds); Add 0.1 part of nonionic polyurethane associative thickener then, stirred 12 hours with stirrer (600～800 rev/mins of rotating speeds).
2. preparation B agent
By ratio of weight and the number of copies, in 35 parts of deionized waters, add 15 parts of γ-glycidyl ether oxygen propyl trimethoxy silicanes, stir more than 2 hours, be water white transparency to solution till.
3. the A agent is added B agent stirring and got uniform water-based zinc-aluminium coating in 10 hours, its dope viscosity (Chai Shi 2# cup) is 30～40 seconds.
4. apply: aforementioned testing standard is pulled; Get coating 50 grams and add in the spray gun, spray, put into the experiment hot-air oven; 300 ℃ of following baking-curings 20 minutes; The coatingsurface metalluster that is silvery white in color, coating is produced Fei Xier D-MPOP thickness tester with moral, and to record coating MV be 3～5 μ m, sticking power adhesive tape method one-level;
Be coated with the testing standard plate with one and carry out secondary spraying and, be cooled to normal temperature 300 ℃ of following baking-curings 20 minutes, the coatingsurface metalluster that is silvery white in color, coating is produced Fei Xier D-MPOP thickness tester with moral and is recorded coating MV 8～9 μ m, sticking power adhesive tape method one-level;
Above-listed spraying on-gauge plate is put into salt-spray cabinet, carry out salt-fog test, can reach 600 hours according to GB/T 10125-1997 standard-requireds.
Get five of on-gauge plates, the commercially available amino-resin coating of compound coating again, thick 10～14 μ m of its compound coating carry out neutral salt spray test (GB/T 10125-1997), can reach 1000 hours.
Embodiment 2
1. preparing A agent
By ratio of weight and the number of copies; Add 18 part 1; Ammediol, 1.0 parts of polyoxyethylene carboxylates (homemade trade mark SG), 1.8 parts of AEOs (homemade trade mark A-20), 4 parts of 200# solvent oils, 20 parts of ultra-fine flake zinc powders of dry-powdered, 5 parts of ultra-fine flakey aluminium powders of dry-powdered; With abundant wetting being uniformly dispersed of Ke Lesi high speed dispersor (1400 rev/mins of rotating speeds); Add 0.2 part of nonionic polyurethane associative thickener then, stirred 12 hours with stirrer (600～800 rev/mins of rotating speeds).
2 method preparation B agent according to embodiment 1
3. the A agent is added B agent stirring and obtained uniform water-based zinc-aluminium coating in 10 hours.
4. getting behind the aforementioned ball blast examination, to be coated with workpiece some, immerse in the masking liquid about 10 seconds, and whizzer (500～1400 rev/mins) gets rid of surplus liquid then, puts into the hot-air oven baking-curing, and the baking-curing temperature is 300 ℃, 20 minutes time.The coatingsurface metalluster that is silvery white in color, coating is produced Fei Xier D-MPOP thickness tester with moral and is recorded coating MV 3～5 μ m, sticking power adhesive tape method one-level; Repeat aforesaid operations, carry out the secondary application and solidify, be cooled to normal temperature, the coatingsurface metalluster that is silvery white in color, coating is produced Fei Xier D-MPOP thickness tester with moral and is recorded coating MV 8～9 μ m, sticking power adhesive tape method one-level;
The zinc-aluminium paint (or soaking) that present embodiment is made is coated with on-gauge plate and examination and is coated with workpiece and puts into salt-spray cabinet, carries out salt-fog test according to GB/T10125-1997 standard-required, can reach 600 hours.
Embodiment 3
1. preparing A agent
By ratio of weight and the number of copies; Add 25 part 1; Ammediol, 1.7 parts of polyoxyethylene carboxylates (homemade trade mark SE-10), 1 part of AEO (homemade trade mark A-20), 0.1 part of mineral oil origin water-based skimmer (BNK-G303), the 30 parts of ultra-fine flake zinc aluminium paste of paste (zinc-aluminium content 89wt%; The mass ratio of zinc-aluminium is 4:1); With abundant wetting being uniformly dispersed of Ke Lesi high speed dispersor (1400 rev/mins of rotating speeds), add 0.2 part of Natvosol thickening material then, stirred 12 hours with stirrer (600～800 rev/mins of rotating speeds).
2. preparation B agent
In 27 parts of deionized waters, add 15 parts of KH-560 silane coupling agents, stir more than 2 hours, be water white transparency to hydrolyzed solution till.
With the A agent add the B agent stir water-borne coatings.
4. getting behind the aforementioned ball blast examination, to be coated with workpiece some, immerse to be coated with in the feed liquid about 10 seconds, and whizzer (500～1400 rev/mins) gets rid of surplus liquid then, puts into the hot-air oven baking-curing, and the baking-curing temperature is 300 ℃, 20 minutes time.The coatingsurface metalluster that is silvery white in color, coating is produced Fei Xier D-MPOP thickness tester with moral and is recorded coating MV 3～5 μ m, sticking power adhesive tape method one-level; Repeat aforesaid operations, carry out the secondary application and solidify, be cooled to normal temperature, the coatingsurface metalluster that is silvery white in color, coating is produced Fei Xier D-MPOP thickness tester with moral and is recorded coating MV 8～9 μ m, sticking power adhesive tape method one-level;
Above-mentioned spray (soaking) standard of being coated with is pulled and examination is coated with workpiece and puts into salt-spray cabinet, carry out salt-fog test 600 hours for qualified according to GB/T10125-1997 GB.
Embodiment 4
1. preparing A agent
In the beaker of 1000ml; Get 20.7 part 1; Ammediol, 1 part of AEO (homemade trade mark 0-10), 1 part of AEO (homemade trade mark A-20), 2 parts of polyoxyethylene polyoxypropylene block polyethers (homemade trade mark X-1005) mix stirring; Add 25 parts of ultra-fine flake zinc aluminium pastes of paste (wherein, zinc-aluminium content is 96wt%, and the zinc-aluminium weight ratio is 3:1); With the abundant wetting homogeneous phase that is dispersed to of Ke Lesi high speed dispersor (1400 rev/mins of rotating speeds); Add 0.3 part of Vltra tears thickening material then, stir with stirrer (600～800 rev/mins of rotating speeds) and dissolved fully to thickening material in 12 hours, guarantee that coating do not have the small-particle polymkeric substance.
2. preparation B agent
In 35 parts of deionized waters, add 15 parts of KH-560 silane coupling agents, stir more than 2 hours, be water white transparency to hydrolyzed solution till.
With the A agent add the B agent stir water-borne coatings.
4. getting behind the aforementioned ball blast examination, to be coated with workpiece some, immerse in the masking liquid about 10 seconds, and whizzer (500～1400 rev/mins) gets rid of surplus liquid then, puts into the hot-air oven baking-curing, and the baking-curing temperature is 300 ℃, 20 minutes time.The coatingsurface metalluster that is silvery white in color, coating is produced Fei Xier D-MPOP thickness tester with moral and is recorded coating MV 3～5 μ m, sticking power adhesive tape method one-level; Repeat aforesaid operations, carry out the secondary application and solidify, be cooled to normal temperature, the coatingsurface metalluster that is silvery white in color, coating is produced Fei Xier D-MPOP thickness tester with moral and is recorded coating MV 8～9 μ m, sticking power adhesive tape method one-level;
With present embodiment zinc-aluminium coating coating workpieces, use commercially available TS-100# inorganic silicate coating compound coating again, its compound coating is thick to be 10～12 μ m, carries out neutral salt spray test (GB/T10125-1997), can reach 1000 hours.
Embodiment 5
1. preparing A agent
By ratio of weight and the number of copies; Add 10 part 1; Ammediol, 15 parts dipropylene glycol, 1.8 parts of polyoxyethylene carboxylates (homemade trade mark SE-10), 1 part of AEO (homemade trade mark A-20), 30 parts of ultra-fine flake zinc aluminium pastes of paste (wherein; Zinc-aluminium content is 92wt%, and the mass ratio of zinc-aluminium is 4:1), with abundant wetting being uniformly dispersed of Ke Lesi high speed dispersor (1400 rev/mins of rotating speeds); Add 0.2 part of Natvosol thickening material then, stirred 12 hours with laboratory stirrer (600～800 rev/mins of rotating speeds).
2. preparation B agent
In 25 parts of deionized waters, add 17 parts of KH-560 silane coupling agents, stir more than 2 hours, be water white transparency to hydrolyzed solution till.
With the A agent add the B agent stir water-borne coatings.
4. getting behind the aforementioned ball blast examination, to be coated with workpiece some, immerse to be coated with in the feed liquid about 10 seconds, and whizzer (500～1400 rev/mins) gets rid of surplus liquid then, puts into the hot-air oven baking-curing, and the baking-curing temperature is 300 ℃, 20 minutes time.The coatingsurface metalluster that is silvery white in color, coating is produced Fei Xier D-MPOP thickness tester with moral and is recorded coating MV 3～5 μ m, sticking power adhesive tape method one-level; Repeat aforesaid operations, carry out the secondary application and solidify, be cooled to normal temperature, the coatingsurface metalluster that is silvery white in color, coating is produced Fei Xier D-MPOP thickness tester with moral and is recorded coating MV 8～9 μ m, sticking power adhesive tape method one-level;
Above-mentioned spray (soaking) standard of being coated with is pulled and examination is coated with workpiece and puts into salt-spray cabinet, carry out salt-fog test, can reach 600 hours according to GB/T 10125-1997 GBs.
Aqueous chromium-free zinc-aluminium coating non-hexavalent chromium of the present invention and lead, mercury, cadmium heavy metal ion compound; Do not contain poisonous organic solvents such as benzene, YLENE, the coating curing temperature is 250-350 ℃, gets final product in 20 minutes; Realized that in the lump coating material production and environment of applications are friendly; Energy-saving and emission-reduction have ensured that operator produce and personnel safety, have accomplished the work situation hygiene.Coating of the present invention had detected through international logical mark SGS already and had identified, met the code requirement of 2000/53/EG of European Union and ROHS instruction fully.
Above content is to combine concrete optimal technical scheme to the further explain that the present invention did, and can not assert that practical implementation of the present invention is confined to these explanations.For the those of ordinary skill of technical field under the present invention, under the prerequisite that does not break away from the present invention's design, can also make some simple deduction or replace, all should be regarded as belonging to protection scope of the present invention.
Claims (7)
1. an aqueous chromium-free zinc-aluminium coating is characterized in that, said aqueous chromium-free zinc-aluminium coating comprises and mix the A agent and the B agent of mixing well when using, and is 100% with the total weight of said A agent and B agent, and said A agent comprises following components in weight percentage:
Emulsifying agent: 1%-5%,
Alcohol: 10%-25%,
Skimmer: 0%-5%,
Thickening material: 0%-0.3%,
Metallic zinc aluminium powder or zinc-aluminium cream: 25%-35%;
Said B agent comprises following components in weight percentage:
Deionized water: 20%-40%,
Silane coupling agent: 10%-20%;
Wherein, said emulsifying agent is selected from one or more in AEO, polyoxyethylene carboxylate, the polyoxyethylene polyoxypropylene block polyether;
Said alcohol is selected from 1, ammediol, dipropylene glycol or their mixture;
Said skimmer is selected from mineral oil origin water-based skimmer or solvent oil;
Said thickening material is selected from one or several in Natvosol, Vltra tears, the nonionic polyurethane associative thickener;
The mass ratio of the zinc-aluminium in said metallic zinc aluminium powder or the zinc-aluminium cream is: 3:1-7:1;
Said silane coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane.
2. aqueous chromium-free zinc-aluminium coating according to claim 1 is characterized in that said metallic zinc aluminium powder is a sheet, and thickness is 0.1-0.3 μ m, and particle diameter is 8-15 μ m, and loose density is 0.9-1.2g/cm
3
3. according to claim 1 or 2 said aqueous chromium-free zinc-aluminium coating, it is characterized in that said alcohol is 1, the mixture of ammediol and dipropylene glycol, and 1, the weight ratio of ammediol and dipropylene glycol is 4:6.
4. according to claim 1 or 2 said aqueous chromium-free zinc-aluminium coating; It is characterized in that; Said emulsifying agent is the mixture of AEO and polyoxyethylene carboxylate; And the weight ratio of AEO and polyoxyethylene carboxylate is 3/7-1, and the HLB value of the mixture of said AEO and said polyoxyethylene carboxylate is 12-15.
5. according to the said aqueous chromium-free zinc-aluminium of claim 4 coating, it is characterized in that Fatty Alcohol(C12-C14 and C12-C18) is C in the said AEO
14～22Synthol, wherein, the polyoxyethylated polymerization degree is 4-20; Lipid acid is C in the said polyoxyethylene carboxylate
16～22Sfas, wherein, the polyoxyethylated polymerization degree is 7-20.
6. preparation method like each described aqueous chromium-free zinc-aluminium coating of claim 1 to 5 is characterized in that said preparation method may further comprise the steps:
Preparing A agent step: said emulsifying agent, alcohol, skimmer, metallic zinc aluminium powder or zinc-aluminium cream are mixed, be uniformly dispersed, add thickening material again, stir with stirrer;
Preparation B agent step: said silane coupling agent is added in the deionized water, be stirred to said solution and be till the water white transparency;
Mixing step: said A agent is added in the said B agent, stir water-based zinc-aluminium coating.
7. preparation method according to claim 6 is characterized in that, in the said preparing A agent step, adopts high speed dispersor during dispersion, and disperseing rotating speed is 1400 rev/mins, and said mixing speed is 600～800 rev/mins.
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