CN104451645A - Trivalent chromium passivation surface treating agent, - Google Patents
Trivalent chromium passivation surface treating agent, Download PDFInfo
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- CN104451645A CN104451645A CN201410742329.5A CN201410742329A CN104451645A CN 104451645 A CN104451645 A CN 104451645A CN 201410742329 A CN201410742329 A CN 201410742329A CN 104451645 A CN104451645 A CN 104451645A
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- China
- Prior art keywords
- trivalent chromium
- acid
- surface treatment
- compound
- treatment agent
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000011651 chromium Substances 0.000 title claims abstract description 44
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 42
- 238000002161 passivation Methods 0.000 title claims abstract description 34
- 239000003795 chemical substances by application Substances 0.000 title abstract description 11
- -1 phosphorus compound Chemical class 0.000 claims abstract description 30
- 239000002253 acid Substances 0.000 claims abstract description 28
- 229910000077 silane Inorganic materials 0.000 claims abstract description 15
- 150000007524 organic acids Chemical class 0.000 claims abstract description 14
- 239000011248 coating agent Substances 0.000 claims abstract description 13
- 238000000576 coating method Methods 0.000 claims abstract description 13
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011737 fluorine Substances 0.000 claims abstract description 12
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 11
- 239000011574 phosphorus Substances 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001845 chromium compounds Chemical class 0.000 claims abstract description 6
- 150000001869 cobalt compounds Chemical class 0.000 claims abstract description 6
- 239000012756 surface treatment agent Substances 0.000 claims description 36
- 229910000831 Steel Inorganic materials 0.000 claims description 26
- 239000010959 steel Substances 0.000 claims description 26
- 210000000981 epithelium Anatomy 0.000 claims description 21
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000174 gluconic acid Substances 0.000 claims description 4
- 235000012208 gluconic acid Nutrition 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 235000011007 phosphoric acid Nutrition 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229920001296 polysiloxane Chemical class 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 230000036647 reaction Effects 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 25
- 230000007797 corrosion Effects 0.000 abstract description 23
- 229910001335 Galvanized steel Inorganic materials 0.000 abstract description 14
- 239000008397 galvanized steel Substances 0.000 abstract description 14
- 238000004383 yellowing Methods 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 150000002697 manganese compounds Chemical class 0.000 abstract 1
- 238000000034 method Methods 0.000 description 29
- 230000008569 process Effects 0.000 description 17
- 238000010422 painting Methods 0.000 description 16
- 239000007769 metal material Substances 0.000 description 13
- 238000002474 experimental method Methods 0.000 description 10
- 238000004381 surface treatment Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 241000919514 Albuginaceae Species 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- 238000005246 galvanizing Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 2
- 229940048102 triphosphoric acid Drugs 0.000 description 2
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-N Salicylic acid Natural products OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- KULZLSHMXVZRKE-UHFFFAOYSA-N chromium perchloric acid Chemical compound [Cr].Cl(=O)(=O)(=O)O KULZLSHMXVZRKE-UHFFFAOYSA-N 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- LAIOKZCTQAIQDM-UHFFFAOYSA-H chromium(3+);diphosphate;heptahydrate Chemical compound O.O.O.O.O.O.O.[Cr+3].[Cr+3].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LAIOKZCTQAIQDM-UHFFFAOYSA-H 0.000 description 1
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N cinnamic acid Chemical compound OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- CMMUKUYEPRGBFB-UHFFFAOYSA-L dichromic acid Chemical compound O[Cr](=O)(=O)O[Cr](O)(=O)=O CMMUKUYEPRGBFB-UHFFFAOYSA-L 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- NTQGILPNLZZOJH-UHFFFAOYSA-N disilicon Chemical compound [Si]#[Si] NTQGILPNLZZOJH-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- XEEVLJKYYUVTRC-UHFFFAOYSA-N oxomalonic acid Chemical compound OC(=O)C(=O)C(O)=O XEEVLJKYYUVTRC-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 150000007965 phenolic acids Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Classifications
-
- 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
- C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium
Landscapes
- Chemical Treatment Of Metals (AREA)
Abstract
The invention discloses a trivalent chromium passivation surface treating agent. The trivalent chromium passivation surface treating agent comprises the following components: (1) 3.0-7.0wt% of a trivalent chromium compound; (2) 0.1-1.0wt% of a cobalt compound; (3) 0.1-1.0wt% of a manganese compound; (4) 10-18wt% of a phosphorus compound; (5) an organic acid which is 0.1-1.0wt% of organic acid comprising carbon, hydrogen and oxygen elements and fluorine-containing acid; (6) 2-10wt% of a silane compound and the balance of water. By the trivalent chromium passivation surface treating agent disclosed by the invention, the surface film formed on the surface of a galvanized steel plate has the advantages of excellent corrosion resistance, top-coat coating adhesion, yellowing resistance and blackening resistance and the defects of poor corrosion resistance and top-coat coating adhesion of the surface film of the galvanized steel plate in the prior art are effectively solved.
Description
Technical field
The present invention relates to a kind of trivalent chromium passivation surface treatment agent, belong to technical field of metal material surface treatment.
Background technology
The metallic substance such as steel plate galvanized and aluminium sheet is widely used in fields such as automobile, building materials and household electric appliances.But the zinc that these metallic substance adopt and aluminium in an atmosphere corrosion can generate the corrosion product being called as white rust, these white rusts have makes metallic substance outward appearance decline, and even the tack of upper paint coating is brought to the shortcoming of negative impact.
Therefore in order to improve the painting adhesion of above-mentioned materials and solidity to corrosion, generally all the main treatment solution containing chromic acid, dichromic acid or other salts can be used to carry out chromic salt process at metal material surface.
But, in recent years due to the raising of environmental consciousness, because 6 valency chromium in the chromate treating solution that uses in metal material surface process have direct harm to human body, so start to have avoided to chromic salt process.And must process especially according to the regulation of water pollution control method during discharge of wastewater containing 6 valency chromium, this relative enterprise becomes the factor increasing cost undoubtedly.Further, the metallic substance of chromic salt process, due to containing chromium, cannot recycle after going out of use, and this has become social problem.
On the other hand, the surface treatment agent containing Weibull or multivalence phenol carboxylic acid is adopted to process steel plate galvanized and surface of aluminum plate, being well-known as the alternative method of chromic salt process.Use tannin aqueous acid to process metallic substance, form protection epithelium by the reaction of Weibull and metallic substance, due to the intrusion of corrosive deposit can be stopped, think and improve solidity to corrosion and painting adhesion.
But, in recent years, along with the high quality of product, solidity to corrosion for epithelium self requires to improve, and also requires the upper paint coating tack of epithelium, therefore simultaneously, Weibull is independent and/or inorganic and with the epithelium of gained, its solidity to corrosion is also insufficient, at present also can not be practical.
So, as the treatment process that can improve these performances, Japanese Patent Laid-Open No. Sho 53-121034 publication is issued, the aqueous solution containing water-dispersible silica and Synolac, trialkoxy silane compound has been coated on metallic surface, after dry, formed the method for coating epithelium.
Also have, Japanese Patent Laid-Open No. Sho 57-44751 publication and Unexamined Patent 1-177380 publication disclose the water soluble resin using carboxyl dipyrryl ketone compound inductor to be formed, to reach the surface treatment method giving metallic substance solidity to corrosion object, and the aqueous solution of carboxyl styrene ene compound and water dispersible doubling body is used to give the corrosion proof method of metallic substance etc.But which kind of method above-mentioned all cannot be formed can substitute chromium hydrochlorate epithelium, has the epithelium of high anti-corrosion and painting adhesion.Japanese Patent Laid-Open 11-106945 gazette publication uses the treatment agent process steel plate galvanized of metal ion and acid, organo-silane coupling agents and water-soluble coincidence thing composition, but solves the problem not yet.
Simultaneously, be provided with the surface treated steel plate of these epitheliums, when being particularly used in household appliances, in order to embody different appearance designs, many times all can carry out powder body coating or solvent application to steel plate, if the tack of these epitheliums and these applications is very poor, film during use, may be caused to peel off, cause value of the product to decline.Meanwhile, if the incomplete words of the solidity to corrosion of steel plate self, can corrode under film, film can be caused equally to peel off.Under such circumstances, must carry out the replacing of product or repairing etc., burden economically becomes large.Therefore, prior art is badly in need of a kind of surface treatment agent for steel plate galvanized, requires that adopting this surface treatment agent to carry out surface-treated steel plate galvanized has excellent solidity to corrosion and the good adhesion with powder body coating, solvent application.
Summary of the invention
The object of this invention is to provide a kind of trivalent chromium passivation surface treatment agent, it contains trivalent chromium and other metallic compounds and specific silane compound, the epithelium using it to be formed at metal material surface, has excellent corrosion resistance, upper painting painting adhesion, yellowing resistance and anti-blackening etc.
Technical scheme of the present invention is as follows:
A kind of trivalent chromium passivation surface treatment agent, it comprises:
The trivalent chromium compound of (1) 3.0 ~ 7.0 % by weight;
The cobalt compound of (2) 0.1 ~ 1.0 % by weight;
The manganic compound of (3) 0.1 ~ 1.0 % by weight;
The phosphorus compound of (4) 10 ~ 18 % by weight;
The organic acid of (5) 0.1 ~ 1.0 % by weight, described organic acid refers to the organic acid of hydrocarbon oxygen element composition and the acid containing fluorine element; With
The silane compound of (6) 2 ~ 10 % by weight,
All the other are water.
Compared with prior art, beneficial effect of the present invention is as follows:
Use trivalent chromium passivation surface treatment agent of the present invention the epithelium that galvanized steel sheet surface is formed have excellent corrosion resistance, on be coated with painting adhesion, yellowing resistance and anti-blackening etc., efficiently solve the defect that epithelium solidity to corrosion is not high and upper painting painting adhesion is not good of steel plate galvanized in prior art.
Certainly, implement arbitrary product of the present invention might not need to reach above-described all advantages simultaneously.
Embodiment
The invention provides a kind of trivalent chromium passivation surface treatment agent, can be applicable to the surface treatment of metallic substance, especially for the surface treatment of steel plate galvanized.
In this article, the scope represented by " numerical value is to another numerical value " is a kind of summary representation avoiding all numerical value enumerated in the description in this scope.Therefore, the record of a certain special value scope, the comparatively fractional value scope containing any number in this numerical range and defined by any number in this numerical range, as expressly write out this any number in the description, comparatively fractional value scope is the same with this.
Trivalent chromium passivation surface treatment agent of the present invention comprises:
The trivalent chromium compound of (1) 3.0 ~ 7.0 % by weight;
The cobalt compound of (2) 0.1 ~ 1.0 % by weight;
The manganic compound of (3) 0.1 ~ 1.0 % by weight;
The phosphorus compound of (4) 10 ~ 18 % by weight;
The organic acid of (5) 0.1 ~ 1.0 % by weight, described organic acid refers to the organic acid that hydrocarbon oxygen element forms and the acid containing fluorine element; With
The silane compound of (6) 2 ~ 10 % by weight,
All the other are water.
The principle of trivalent chromium passivation surface treatment agent of the present invention is as follows:
1. react: Zn+2H
+→ Zn
+++ H
2
2. react: Cr
++++ PO
4 ---→ CrPO
4
3. react:
4. form zinc phosphate/chromium rete:
Wherein, the poor corrosion resistance of the Plessy's green that the 2nd step reaction is formed, the ZnCrF that the 3rd step reaction is formed
2pO
4corrosion resistance and good, and front three-step reaction and oven dry plate temperature (PMT) temperature have relation, trivalent chromium passivation surface treatment agent of the present invention is arranged on after on steel plate galvanized, carries out under heating its process of drying, and Heating temperature is good at 70 ~ 150 DEG C.The galvanized steel sheet surface handled well there will be blushing after touching water or shaping dope, and major cause is because the reaction of galvanized steel sheet surface does not terminate completely, produces excessive erosion caused substrate.And the Heating temperature of above-mentioned oven dry can ensure that blushing is less likely to occur the galvanized steel sheet surface after processing.
Wherein, this trivalent chromium passivation surface treatment agent is with coating chrome content 30 ~ 80mg/m
2, total thickness is that the epithelium of 0.1 ~ 0.8 μm is arranged on the surface of steel plate galvanized.Preferably coating chrome content is 40-60mg/m further
2.
The trivalent chromium compound that the present invention is used and cobalt compound, manganic compound have no particular limits, can be such as that the soluble inorganic compound of respective element is as nitrate, or by insoluble chemical compound and strong acid react dissolve after is formed, as the compound such as chromic acid, manganous carbonate conversion and the compound etc. that obtains separately under certain condition respectively.
The organic acids of described hydrocarbon oxygen element composition is as being oxalic acid, gluconic acid, citric acid etc.
The described acid containing fluorine element can be the mineral acid containing fluorine element such as hydrofluotitanic acid, silicofluoric acid, hydrofluoric acid, fluorine zirconic acid.The organic acid of described hydrocarbon oxygen element composition and the described acid containing fluorine element can with any than mixing.
Described phosphorus compound is at least the one of ortho-phosphoric acid, Tripyrophosphoric acid or organic phosphonic compound.Wherein, Tripyrophosphoric acid can use tetra-sodium, triphosphoric acid, three metaphosphoric acids, four metaphosphoric acids, hexa metaphosphoric acid or its alkaline metal salt and ammonium salt.
Described silane compound can use silicomethane, silicoethane, the elementary composition silane compound of the silicon hydrocarbon such as Trisilicopropane, and/or the silicone compounds of sily oxide, trisiloxanes etc.
Wherein, the phosphorus compound in surface treatment agent of the present invention plays the rust-preventive agent effect of steel plate galvanized, can improve surface treatment agent of the present invention and cover the solidity to corrosion being arranged on the organic composite film that galvanized steel sheet surface obtains.And the scope that the combined amount of phosphorus compound accounts for 10 ~ 18 % by weight is good.If the combined amount of phosphorus compound is below 10 % by weight, then the effect as rust-preventive agent declines, the solidity to corrosion imperfection of the organic composite film causing surface treatment agent of the present invention to obtain at galvanized steel sheet surface.In addition, if the combined amount of phosphorus compound is more than 18 % by weight, then superfluous phosphorus compound will dissolve, and be coated with painting adhesion on likely reducing.
The linking agent that silane compound of the present invention plays described organic composite film also has the effect of tackiness agent, can improve all performances such as the solidity to corrosion of organic composite film, upper painting painting adhesion, anti-blackening.Wherein, the scope accounting for 2 ~ 10 % by weight in the combined amount of silane compound is good.If the combined amount of silane compound is below 2 % by weight, then the effect of tackiness agent declines, each performance imperfection of organic composite film.In addition, if the combined amount of silane compound is more than 10 % by weight, then the much higher hard of epithelium, may cause processibility and upper painting painting adhesion to decline.Therefore, according to the repeatedly research and analysis of the present inventor, determine that the scope that silane compound is suitable for relatively is 2 ~ 10 % by weight.
The method utilizing trivalent chromium passivation surface treatment agent of the present invention to form epithelium on steel plate galvanized is not particularly limited, and such as pickling process, spraying process and rolling method etc. can be suitable for.In addition, about treatment temp, treatment time, also there is no particular limitation.The kind, specification, shape etc. of the steel plate galvanized that the present invention is suitable for are not particularly limited, and such as hot-dip galvanizing sheet steel, electrogalvanizing steel plate etc. all can be selected.
Below in conjunction with specific embodiment, set forth the present invention further.Should be appreciated that, these embodiments only for illustration of the present invention, and are not intended to limit the scope of the invention.The improvement made according to the present invention of those skilled in the art and adjustment, still belong to protection scope of the present invention in actual applications.
Embodiment 1
Being described as follows of experiment material, its method for decontaminating surfaces and trivalent chromium passivation surface treatment agent that the present embodiment is used.Experiment material used: steel plate galvanized, thickness of slab 0.6mm hot-dip galvanizing sheet steel (GI), the target adhesion amount 40mg/m of the chromium of trivalent chromium passivation surface treatment agent
2.
Before trivalent chromium passivation surface treatment agent of the present invention is arranged on galvanized steel sheet surface, according to usual means, metal sheet is cleaned as follows: in adopting the surface of above-mentioned steel plate galvanized, alkali cleaner solution (drug concentration: 20g/ litre) cleans, treatment temp: 60 DEG C, treatment time: 20 seconds, carry out spraying process, the rubbish of surface attachment and oil are removed.Fall the remaining alkali in surface by washed with de-ionized water afterwards to divide, the surface of supplied experiment material is cleaned.Then, adopt pickling process, spraying process or rolling method that trivalent chromium passivation surface treatment agent of the present invention is arranged on galvanized steel sheet surface, dry in a heated condition afterwards, Heating temperature is at 70 ~ 150 DEG C.
The trivalent chromium passivation surface treatment agent of the present embodiment has following several formula:
Formula one:
The chromium nitrate of (1) 3.0 % by weight;
The Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES of (2) 1.0 % by weight;
The manganous nitrate of (3) 0.1 % by weight;
The ortho-phosphoric acid of (4) 18 % by weight;
The oxalic acid of (5) 1.0 % by weight and the mixture of hydrofluoric acid, its mesoxalic acid and hydrofluoric acid mix with 1:2 volume ratio; With
The silicomethane of (6) 10 % by weight.
Formula two:
The chromium sulphate of (1) 7.0 % by weight;
The cobalt chloride of (2) 0.1 % by weight;
The manganous sulfate of (3) 1.0 % by weight;
The triphosphoric acid of (4) 10 % by weight;
The gluconic acid of (5) 0.1 % by weight and silicofluoric acid mixture, wherein gluconic acid and silicofluoric acid mix with 1:1 volume ratio; With
The sily oxide of (6) 2 % by weight.
Formula three:
The chromium chloride of (1) 4.0 % by weight;
The rose vitriol of (2) 0.5 % by weight;
The Manganous chloride tetrahydrate of (3) 0.3 % by weight;
Three metaphosphoric acids of (4) 14 % by weight;
The citric acid of (5) 0.8 % by weight and fluorine zirconic acid, wherein citric acid and fluorine zirconic acid mix with 3:1 volume ratio; With
The Trisilicopropane of (6) 6 % by weight.
Formula four:
The perchloric acid chromium of (1) 6.0 % by weight;
The Cobaltous diacetate of (2) 0.8 % by weight;
The manganous nitrate of (3) 0.7 % by weight;
The tetra-sodium of (4) 12 % by weight;
The citric acid of (5) 0.3 % by weight and hydrofluotitanic acid, wherein citric acid and the mixing of hydrofluotitanic acid 1:5 volume ratio; With
The trisiloxanes of (6) 4 % by weight.
The performance of the epithelium formed at galvanized steel sheet surface above several formula is evaluated by following test method.
1. solidity to corrosion
By salt mist experiment (JISZ2371), visual judgement resistance to white rust, to arrive 5% time spent with white rust area and evaluate.
2. coating adhesion
Experiment surface treatment steel plate galvanized carries out the application of following condition and carries out film attachment experiment.Spraying polyurethane powder, baking condition: 180 DEG C × 20 points, form the film of 40 ~ 60 μm.
2.1 painting adhesion
1. cross draw lattice experiment on above-mentioned polyurethane coating film draw 100 length and width be the grid of 1mm after peel off with scotch tape, evaluated by the remaining number of film.
2. shock test is impacted, depending on its degree of splitting with Apparatus for Impacting at low-temp 50cm place on film.
3. anti-blackening
To test and be cut into plural block with surface treatment steel plate galvanized, what same brassboard cut is a pair between two relatively, and 5 ~ 10 to overlap, after plastic wrapping paper bale packing, 4 angles screws down, clamps with torque spanner with the loading of 0.67Kgf.cm; Then, 50 DEG C, put 120 hours in the moistening case of the relative humidity of 95% after take out, visual judgement is carried out to the black change situation of coincidence part.
4. yellowing resistance
Be placed in baking oven by experiment surface treatment galvanized steel sheet surface, 240 DEG C, 30min baking, visual observation surface changes and evaluates, and measures Δ E before and after its baking with color difference meter.
5. alkali resistance
Experiment surface treatment galvanized steel sheet surface is placed in the grease-removing agent of certain basicity, at 50 ~ 60 DEG C, 2min dipping, takes out and observe its surface change, or measure surface of steel plate chrome content change before and after process.
Experimentally result, the performance of the above-mentioned formula gained epithelium of the present embodiment is as follows:
Solidity to corrosion: within minimum 72 hours white rusts 5%;
General coating is good; Application cross cut test: 100% passes through; Application shock test: good;
Anti-blackening: minimum 120h is without white rust;
Anti-yellowing property: 240 DEG C × 30min condition Xia ， ⊿ E < 4;
The alkali cleaning of resistance to PH≤10.
Embodiment 2
The trivalent chromium passivation surface treatment agent provided with the formula one of embodiment 1 carries out the experiment of the target adhesion amount of DIFFERENT Cr, and result is as following table 1 and table 2.
Table 1
Table 2
From above-mentioned data, the present embodiment uses chromium coating amount 40-45mg/m
2, the result of salt-fog test and constant moisture test shows that the epithelium of the galvanized steel sheet surface of this embodiment gained has good solidity to corrosion and anti-blackening.
As fully visible; trivalent chromium passivation surface treatment agent of the present invention is after carrying out surface treatment formation epithelium to steel plate galvanized; the property such as the solidity to corrosion of described epithelium, upper painting painting adhesion, anti-blackening, yellowing resistance are all very excellent; even technical solution of the present invention is as the schemes of countermeasures to the social concern such as environment protection and recycling; also extremely effective, effect is very large in practical.
Under the instruction of the present invention and above-described embodiment, those skilled in the art are easy to predict, cited or each raw material that exemplifies of the present invention or its equivalent alterations, each working method or its equivalent alterations can realize the present invention, and the parameter bound value of each raw material and working method, interval value can realize the present invention, do not enumerate embodiment at this.
Claims (9)
1. a trivalent chromium passivation surface treatment agent, is characterized in that, it comprises:
The trivalent chromium compound of (1) 3.0 ~ 7.0 % by weight;
The cobalt compound of (2) 0.1 ~ 1.0 % by weight;
The manganic compound of (3) 0.1 ~ 1.0 % by weight;
The phosphorus compound of (4) 10 ~ 18 % by weight;
The organic acid of (5) 0.1 ~ 1.0 % by weight, described organic acid is the organic acid of hydrocarbon oxygen element composition and the acid containing fluorine element; With
The silane compound of (6) 2 ~ 10 % by weight,
All the other are water.
2. trivalent chromium passivation surface treatment agent as claimed in claim 1, it is characterized in that, described trivalent chromium passivation surface treatment agent is with coating chrome content 30 ~ 80mg/m
2, total thickness is that the epithelium of 0.1 ~ 0.8 μm is arranged on the surface of steel plate galvanized.
3. trivalent chromium passivation surface treatment agent as claimed in claim 2, it is characterized in that, it is 40 ~ 60mg/m further that described trivalent chromium passivation surface treatment agent is coated to chrome content
2.
4. trivalent chromium passivation surface treatment agent as claimed in claim 2 or claim 3, it is characterized in that, described trivalent chromium passivation surface treatment agent is arranged on after on steel plate galvanized, carries out heating, drying to it, and Heating temperature is 70 ~ 150 DEG C.
5. trivalent chromium passivation surface treatment agent as claimed in claim 1, it is characterized in that, described phosphorus compound is at least the one of ortho-phosphoric acid, Tripyrophosphoric acid or organic phosphonic compound.
6. trivalent chromium passivation surface treatment agent as claimed in claim 1, is characterized in that, described silane compound is the elementary composition silane compound of silicon hydrocarbon and/or silicone compounds.
7. trivalent chromium passivation surface treatment agent as claimed in claim 1, is characterized in that, described trivalent chromium compound and cobalt compound, manganic compound are selected from the soluble salt of respective element, or by difficulty soluble salt or can not the corresponding solvend that obtains of molten salt react ion.
8. trivalent chromium passivation surface treatment agent as claimed in claim 1, is characterized in that, the organic acid of described hydrocarbon oxygen element composition is selected from oxalic acid, gluconic acid or citric acid.
9. the trivalent chromium passivation surface treatment agent as described in claim 1 or 8, is characterized in that, the described acid containing fluorine element be selected from hydrofluotitanic acid, silicofluoric acid, hydrofluoric acid, fluorine zirconic acid one or more.
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| CN112930419A (en) * | 2018-10-24 | 2021-06-08 | Posco公司 | Surface treatment solution composition containing trivalent chromium and inorganic compound, and method for producing hot-dip galvanized steel sheet surface-treated with the same |
| CN115397926A (en) * | 2020-04-15 | 2022-11-25 | 汉高股份有限及两合公司 | Anti-blackening coating composition |
| WO2024112286A1 (en) * | 2022-11-21 | 2024-05-30 | Borcelik Celik San. Tic. A.S. | A coating material that provides anti-corrosive effect and that improves dust prevention and fingerprint prevention characteristics for steel material surfaces that have been subjected to zinc coating processes, and a steel that comprises said coating material |
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| CN111601911A (en) * | 2017-11-13 | 2020-08-28 | Posco公司 | Trivalent chromium-containing solution composition for treating surface of steel sheet, hot-dip galvanized steel sheet surface-treated with the composition, and method for manufacturing hot-dip galvanized steel sheet |
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| CN111511963A (en) * | 2017-12-27 | 2020-08-07 | 日本帕卡濑精株式会社 | Surface treatment agent for metal material, metal material having surface treatment film, and method for producing same |
| CN112930419A (en) * | 2018-10-24 | 2021-06-08 | Posco公司 | Surface treatment solution composition containing trivalent chromium and inorganic compound, and method for producing hot-dip galvanized steel sheet surface-treated with the same |
| CN112930419B (en) * | 2018-10-24 | 2023-06-09 | 浦项股份有限公司 | Surface treatment solution composition and method for producing hot dip galvanized steel sheet surface-treated with the same |
| US12221702B2 (en) | 2018-10-24 | 2025-02-11 | Posco Co., Ltd | Surface treatment solution composition containing trivalent chromium and inorganic compound, and method for manufacturing hot dip galvanized steel sheet surface-treated using same |
| CN115397926A (en) * | 2020-04-15 | 2022-11-25 | 汉高股份有限及两合公司 | Anti-blackening coating composition |
| CN115397926B (en) * | 2020-04-15 | 2024-07-09 | 汉高股份有限及两合公司 | Anti-blackening coating composition |
| WO2024112286A1 (en) * | 2022-11-21 | 2024-05-30 | Borcelik Celik San. Tic. A.S. | A coating material that provides anti-corrosive effect and that improves dust prevention and fingerprint prevention characteristics for steel material surfaces that have been subjected to zinc coating processes, and a steel that comprises said coating material |
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