CN112853336A - Chromium-free surface treating agent for aluminum can cover packaging material, and preparation method and passivation process thereof - Google Patents
Chromium-free surface treating agent for aluminum can cover packaging material, and preparation method and passivation process thereof Download PDFInfo
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- CN112853336A CN112853336A CN202011628723.8A CN202011628723A CN112853336A CN 112853336 A CN112853336 A CN 112853336A CN 202011628723 A CN202011628723 A CN 202011628723A CN 112853336 A CN112853336 A CN 112853336A
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 67
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 238000002161 passivation Methods 0.000 title claims abstract description 64
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000005022 packaging material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229920005989 resin Polymers 0.000 claims abstract description 33
- 239000011347 resin Substances 0.000 claims abstract description 33
- 229910000077 silane Inorganic materials 0.000 claims abstract description 33
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 29
- 239000010703 silicon Substances 0.000 claims abstract description 29
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 claims abstract description 20
- 239000004254 Ammonium phosphate Substances 0.000 claims abstract description 17
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims abstract description 17
- 235000019289 ammonium phosphates Nutrition 0.000 claims abstract description 17
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims abstract description 17
- FENFUOGYJVOCRY-UHFFFAOYSA-N 1-propoxypropan-2-ol Chemical compound CCCOCC(C)O FENFUOGYJVOCRY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002738 chelating agent Substances 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims description 30
- 239000011248 coating agent Substances 0.000 claims description 29
- 239000000758 substrate Substances 0.000 claims description 27
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 15
- 239000012756 surface treatment agent Substances 0.000 claims description 15
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 11
- 229910052731 fluorine Inorganic materials 0.000 claims description 11
- 239000011737 fluorine Substances 0.000 claims description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000007865 diluting Methods 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 4
- JSYPRLVDJYQMAI-ODZAUARKSA-N (z)-but-2-enedioic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)\C=C/C(O)=O JSYPRLVDJYQMAI-ODZAUARKSA-N 0.000 claims description 3
- HMXFDVVLNOFCHW-UHFFFAOYSA-N 1-butyl-2,2-dimethoxyazasilolidine Chemical compound CCCCN1CCC[Si]1(OC)OC HMXFDVVLNOFCHW-UHFFFAOYSA-N 0.000 claims description 3
- BRNBYPNQQNFBEX-UHFFFAOYSA-N 2,2-dimethoxy-1,6,2-diazasilocane Chemical compound CO[Si]1(OC)CCCNCCN1 BRNBYPNQQNFBEX-UHFFFAOYSA-N 0.000 claims description 3
- BJMVMCLSNWRFSD-UHFFFAOYSA-N 5-ethyl-4,6,11-trioxa-1-aza-5-silabicyclo[3.3.3]undecane Chemical compound O1CCN2CCO[Si]1(CC)OCC2 BJMVMCLSNWRFSD-UHFFFAOYSA-N 0.000 claims description 3
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 239000000839 emulsion Substances 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 229920000141 poly(maleic anhydride) Polymers 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 229920005749 polyurethane resin Polymers 0.000 claims description 3
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- BKLGNGGEJNHIQT-UHFFFAOYSA-N prop-2-enoic acid;silicon Chemical compound [Si].OC(=O)C=C BKLGNGGEJNHIQT-UHFFFAOYSA-N 0.000 claims description 2
- 238000007761 roller coating Methods 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 abstract description 11
- 238000005260 corrosion Methods 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000002131 composite material Substances 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 55
- 239000003973 paint Substances 0.000 description 23
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 20
- 239000002244 precipitate Substances 0.000 description 20
- 238000005406 washing Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 230000007062 hydrolysis Effects 0.000 description 8
- 238000006460 hydrolysis reaction Methods 0.000 description 8
- 229910000838 Al alloy Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 239000008399 tap water Substances 0.000 description 6
- 235000020679 tap water Nutrition 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 238000010411 cooking Methods 0.000 description 4
- 238000007667 floating Methods 0.000 description 4
- 239000000413 hydrolysate Substances 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 235000013361 beverage Nutrition 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 230000003749 cleanliness Effects 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 239000013527 degreasing agent Substances 0.000 description 3
- 238000005237 degreasing agent Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 235000015110 jellies Nutrition 0.000 description 3
- 239000008274 jelly Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920003225 polyurethane elastomer Polymers 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- -1 vanadyl carboxylate Chemical class 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
- C23C22/361—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing titanium, zirconium or hafnium compounds
-
- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
-
- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
- C23C22/76—Applying the liquid by spraying
Abstract
The invention discloses a chromium-free surface treating agent for an aluminum can cover packaging material, a preparation method and a passivation process thereof, wherein the chromium-free surface treating agent comprises the following components in percentage by mass: ammonium fluotitanate, ammonium phosphate, propylene glycol propyl ether, azacyclo-silane, water-soluble organic silicon modified resin, chelating agent, organic carboxylic acid vanadyl complex and pure water or deionized water. The production steps are as follows: respectively dissolving ammonium fluotitanate and ammonium phosphate in water; slowly adding an ammonium fluotitanate solution into the ammonium phosphate solution while dispersing; adding propylene glycol propyl ether, and dispersing uniformly; and cooling, and adding nitrogen aza-azacyclo-silane, organic silicon modified resin solution, organic carboxylic acid vanadyl complex solution and chelating agent while dispersing in sequence to obtain the chromium-free surface treating agent. The advantages include: the composite film with the organic-inorganic mixed structure formed on the surface of the base material is stable, does not generate color difference, has good corrosion resistance and few pollutants in the passivation solution, and can prolong the service time of the bath solution.
Description
Technical Field
The invention relates to the technical field of surface treatment of packaging materials, in particular to a surface treatment technology of an aluminum can cover packaging material.
Background
The rapid development of the beverage industry leads to the dramatic increase of the demand of various pop can packaging materials, in particular to aluminum can cover materials. The aluminum can lid requires a surface treatment to prevent the metal ions from dissolving into the beverage. The common surface treatment is to passivate the surface of the raw material strip of the aluminum can cover to form a chemical conversion film, and then to coat the chemical conversion film with organic paint, so as to achieve the purposes of corrosion resistance and beautiful appearance. The passivation treatment effect is an important factor influencing the corrosion resistance, coating adhesion and appearance of the aluminum can cover. However, the passivation treatment technology is environmentally friendly and the performance of the aluminum can lid itself has many problems, such as:
1) the waste water contains heavy metal components such as chromium;
2) during production, the aluminum material is difficult to avoid corrosion, precipitates are generated in the passivating agent, the service cycle of the passivating tank is short, and the replacement is frequent;
3) after passivation, the aluminum can cover has obvious color difference;
4) the passivation speed is slow, and the drying energy consumption is high.
In order to solve the above problems, the beverage packaging industry is in need of developing new passivation treatment agents to be applied to the production of aluminum can lids.
Disclosure of Invention
The invention aims to provide a chromium-free surface treating agent for an aluminum can cover packaging material and a preparation method thereof, and aims to solve the problems that in the prior art, heavy metal chromium polluting the environment exists in waste water after passivation treatment of an aluminum can cover, aluminum materials are easy to corrode during passivation, and the aluminum can cover has obvious color difference.
The invention also aims to provide a passivation process using the chromium-free surface treatment agent for the aluminum can cover packaging material, so as to solve the problems of low passivation speed and high drying energy consumption.
In order to achieve the purpose, the invention adopts the following technical scheme:
a chromium-free surface treating agent for an aluminum can lid packaging material comprises the following components in percentage by mass:
further, the air conditioner is provided with a fan,
the azacyclo-silane is one or more than two of 5-ethyl-4, 6, 11-trioxa-1-aza-5-silabicyclo [3.3.3] undecane, N-N-butyl-aza-2, 2-dimethoxy silacyclopentane, 2-diethoxy-1- (trimethylsilyl) -1-aza-2-silacyclopentane and 2, 2-dimethoxy-1, 6-diaza-2-silacyclooctane.
Further, the air conditioner is provided with a fan,
the water-soluble organic silicon modified resin is one or more of water-soluble organic silicon acrylic acid modified resin, water-soluble organic silicon modified epoxy resin and water-soluble organic silicon modified polyurethane resin.
Further, the air conditioner is provided with a fan,
the chelating agent is one or more of low molecular polyacrylic acid, maleic acid-acrylic acid copolymer and hydrolyzed polymaleic anhydride.
Further, the air conditioner is provided with a fan,
the organic carboxylic acid vanadyl complex is one or two of vanadyl oxalate and vanadyl acetylacetonate.
A preparation method of a chromium-free surface treating agent for an aluminum can lid packaging material is characterized by comprising the following steps:
the method comprises the following steps:
(1) dissolving ammonium fluotitanate in water to prepare an ammonium fluotitanate solution for later use; dissolving ammonium phosphate in pure water to prepare ammonium phosphate solution;
(2) slowly adding ammonium fluotitanate solution into the ammonium phosphate solution while dispersing, uniformly dispersing to prepare fluorine-containing titanium phosphate solution,
mixing ammonium phosphate and ammonium fluotitanate in a proper proportion and forming a nano fluorine-containing titanium phosphate suspension under the conditions of fluorine and ammonium salt under the action of high-speed dispersion;
(3) adding propylene glycol propyl ether into the fluorine-containing titanium phosphate solution, and uniformly dispersing;
(4) cooling the solution prepared in the step (3), and adding azacyclo-silane while dispersing;
(5) dissolving water-soluble organic silicon modified resin in water to obtain an organic silicon modified resin solution, and adding the organic silicon modified resin solution into the liquid in the step (4) while dispersing;
(6) dissolving an organic carboxylic acid vanadyl complex in water to obtain an organic carboxylic acid vanadyl complex solution, adding the organic carboxylic acid vanadyl complex solution into the solution obtained in the step (5), and uniformly dispersing;
(7) and (4) slowly adding a chelating agent into the solution obtained in the step (6), and uniformly dispersing to obtain the chromium-free surface treating agent.
Preferably, the first and second electrodes are formed of a metal,
and (3) in the step (2), the dispersion speed is 800-1200 r/min in the process of adding the ammonium fluotitanate solution, the solution is gradually changed into white emulsion, and the solution is continuously dispersed for 20-30 minutes at the rotating speed of 300-500 r/min after the addition.
Preferably, the first and second electrodes are formed of a metal,
and (4) cooling the solution to 10-15 ℃, adding azacyclo-silane by using a metering pump according to the adding time of 3 hours, and dispersing at the speed of 800-1200 r/min while adding azacyclo-silane.
After silane hydrolysis, partial hydrolysate can graft the nano-scale titanium phosphate particles formed in the step (2), so that the condition that the adhesion force of titanium phosphate in passivation is poor is improved. The azacyclo-silane is hydrolyzed at 10-15 ℃ under an acidic condition, so that colloidal precipitate formed at the temperature of more than 20 ℃ and precipitate generated by larger particles formed with titanium phosphate are avoided. The metering pump is used for adding the silane-grafted titanium phosphate particles, so that the heat generated by the reaction can be effectively controlled, and meanwhile, the grafted titanium phosphate particles after the silane is hydrolyzed are controlled. The propylene glycol propyl ether can replace alcohol to provide an environment beneficial to silane hydrolysis, can effectively disperse silane hydrolysate and grafted titanium phosphate particles, and can improve the condition that components are stored at normal temperature to prevent precipitates.
Preferably, the first and second electrodes are formed of a metal,
the weight ratio of the water-soluble organic silicon modified resin to the water in the step (5) is 30-50: 100, adding the organic silicon modified resin solution into the liquid in the step (4) by using a metering pump according to the adding time of 30 minutes, adding the organic silicon modified resin solution, dispersing at the speed of 800-1200 r/min, and continuing to disperse for 15 minutes after the adding is finished;
in the step (6), the weight ratio of the organic carboxylic acid vanadyl complex to the water is 3: and (100) adding the organic carboxylic acid vanadyl complex solution into the liquid in the step (5) by using a metering pump according to the addition time of 30 minutes, and continuing to disperse for 15 minutes after the addition is finished.
A passivation process using the chromium-free surface treatment agent for aluminum can lid packaging material, comprising the steps of:
(1) passivating and pretreating an aluminum substrate;
(2) diluting the chromium-free surface treating agent by using deionized water, wherein the weight ratio of the deionized water to the chromium-free surface treating agent is 5-10: 1, adjusting the pH value to 4-5 by using hydrofluoric acid or ammonia water;
(3) passivating the aluminum substrate by a roller coating or soaking squeezing or spraying squeezing process, wherein the treatment time of the chromium-free surface treating agent is 1-5 seconds;
(4) and baking the passivated aluminum substrate in a baking oven at 90 ℃ for 5-8 seconds until no obvious liquid residue exists on the surface, wherein the temperature of the plate reaches 60-80 ℃.
The advantages of the invention include:
1. the ammonium fluotitanate and the silane can form a passivation film mainly comprising a titanium polymer on an aluminum substrate under the acidic condition;
2. the ammonium fluotitanate and the ammonium phosphate can form nano-scale particles, and then generate a synergistic effect with the added silane, so that a composite film with an organic-inorganic mixed framework, which can simultaneously give consideration to the coating adhesive force and improve the corrosion resistance of the base material, can be formed on the surface of the base material; the preparation process of the nano-scale particles formed by the ammonium fluotitanate and the ammonium phosphate is simple, the long-time reaction is not required to be heated, the stability is high, and the production and the use are simple and convenient;
3. the volatility and boiling point of the propylene glycol propyl ether are far higher than those of ethanol and methanol which are commonly used for silane hydrolysis, the propylene glycol propyl ether is stable in aqueous solution, the toxicity of the propylene glycol propyl ether is lower than that of the ethanol and the methanol, and the safety, the stability and the effect of the propylene glycol propyl ether on silane hydrolysis are higher than those of the ethanol and the methanol;
4. the azacyclo-silane has high hydrolysis degree and high activity, can generate polymerization with nano-particles formed by ammonium fluotitanate and ammonium phosphate to generate synergistic action, has good high-temperature resistance after passivation film forming, and can stably generate no color difference after high-temperature cooking and acid cooking after coating;
5. the organic silicon modified resin can further enhance the corrosion resistance of the passive film;
6. the organic carboxylic acid vanadyl complex can accelerate inorganic titanium in a passivation film to form a passivation layer on the surface of an aluminum substrate, and can rapidly promote resin and silane to be crosslinked and cured in the passivation process, so that the time required by passivation is greatly shortened; meanwhile, the organic vanadium oxocarboxylate complex has a slow release effect on the aluminum substrate under the condition of pH 4-5, so that the corrosion effect of the passivator on the aluminum substrate is reduced, the color difference of the aluminum plate surface caused by the uneven passivation film is prevented, the pollutants in the passivation solution are reduced, and the service time of the bath solution is prolonged;
7. the chelating agent can further reduce the corrosion of the passivating agent to the aluminum substrate under the acidic condition, and can simultaneously corrode aluminum alloy components (metal ions) dissolved in the passivating solution during complexing passivation, thereby preventing floccules or precipitates in the bath solution from covering the surface of the aluminum substrate to cause appearance defects during passivation, and prolonging the service life of the bath solution.
Detailed Description
The present invention will be described in detail with reference to specific embodiments, which are illustrative of the present invention and are not to be construed as limiting the present invention.
Example 1
A chromium-free surface treatment agent for an aluminum can lid packaging material comprises the following components in percentage by mass as shown in the following table 1:
TABLE 1
The preparation method of the chromium-free surface treating agent comprises the following steps:
(1) dissolving ammonium fluotitanate in water to prepare an ammonium fluotitanate solution for later use; dissolving ammonium phosphate in pure water to prepare ammonium phosphate solution; if pure water is used, the conductivity of the pure water is less than 10 ms/cm;
(2) slowly adding an ammonium fluotitanate solution into the ammonium phosphate solution while dispersing, wherein the dispersing speed is 800-1200 r/min, the solution gradually becomes a white emulsion, and continuously dispersing for 20-30 minutes at the rotating speed of 300-500 r/min after the addition to prepare a fluorine-containing titanium phosphate solution; mixing ammonium phosphate and ammonium fluotitanate in proportion and forming a nano fluorine-containing titanium phosphate suspension under the conditions of fluorine and ammonium salt under the action of a high-speed dispersing machine;
then, a small sample is taken to detect that the pH value is between 3.0 and 4.5, the sample is kept stand for 30 minutes under the conditions that the temperature is more than or equal to 5 ℃ and less than or equal to 20 ℃, and the solution is in a suspension state;
(3) adding propylene glycol propyl ether into the fluorine-containing titanium phosphate solution, and uniformly dispersing;
(4) cooling the solution prepared in the step (3) to 10-15 ℃, sequentially adding N-N-butyl-aza-2, 2-dimethoxy silacyclopentane and 2, 2-dimethoxy-1, 6-diaza-2-silacyclooctane by using a metering pump according to the total adding time of 3 hours, and dispersing at the speed of 800-1200 r/min while adding;
after silane hydrolysis, partial hydrolysate can be grafted with nano-scale titanium phosphate particles, so that the condition that the adhesion force of titanium phosphate is poor in passivation is improved. The azacyclo-silane is hydrolyzed under acidic condition, certain heat is generated in the silane hydrolysis process, and the temperature is higher than 20 ℃, so that the azacyclo-silane is easy to react violently to generate crosslinking to form colloidal precipitate and form larger particles with titanium phosphate to generate precipitate. The temperature of the solution is 10-15 ℃, and the heat generated by the reaction can be effectively controlled by adding the silane through a metering pump, so that the overhigh temperature can be avoided, and the titanium phosphate particles grafted after the silane is hydrolyzed can be controlled by adding the silane through the metering pump;
the propylene glycol propyl ether can replace alcohol to provide an environment beneficial to silane hydrolysis, can effectively disperse silane hydrolysate and grafted titanium phosphate particles, and can prevent the components from generating precipitates when stored at normal temperature;
(5) dissolving organic silicon modified resin in water, wherein the weight ratio of the organic silicon modified resin to the water is 30-50: 100, obtaining an organic silicon modified resin solution, adding the organic silicon modified resin solution into the liquid in the step (4) by using a metering pump according to the adding time of 30 minutes, effectively controlling the adding speed and the adding amount, preventing the adding speed from being too high and the adding amount from being too high to form a cross-linked precipitate, adding the organic silicon modified resin solution, dispersing at the speed of 800-1200 r/min, and continuing to disperse for 15min after the adding is finished;
after dispersing for 15 minutes, taking a small sample, standing at normal temperature, checking and determining that the solution is uniform, has no precipitate, has no layering and has no floating jelly;
(6) dissolving an organic carboxylic acid vanadyl complex in water, wherein the weight ratio of the organic carboxylic acid vanadyl complex to the water is 3: 100, obtaining an organic carboxylic acid vanadyl complex solution, adding the organic carboxylic acid vanadyl complex solution into the liquid in the step (5) by using a metering pump according to the adding time of 30 minutes, and continuing to disperse for 15 minutes after the adding is finished;
after dispersing for 15 minutes, taking a small sample, standing at normal temperature, checking and determining that the solution is uniform, has no precipitate, has no layering and has no floating jelly;
(7) slowly adding a chelating agent into the solution obtained in the step (6), and uniformly dispersing to obtain the chromium-free surface treating agent;
standing at normal temperature to confirm that the solution is uniform, has no precipitate, no layering and no floating jelly.
And (4), adding by adopting a metering pump in the steps (5) and (6), the adding speed and the adding amount can be effectively controlled, the phenomenon that the adding speed is too high and the adding amount is too high to form a cross-linked precipitate is prevented, and meanwhile, the process standard can be established by controlling the feeding of the metering pump, so that the method is more suitable for large-batch standardized production.
And the above steps, the components are added in sequence, so that a foundation can be provided for the conditions of no generation of precipitates, floccules, layering or floating objects and the like, and the balance is easily damaged due to different sequences, so that the abnormity occurs in the preparation process and the product quality is influenced.
The passivation step comprises:
(1) aluminum substrate passivation pretreatment: degreasing and deoiling 0.32 mm-thick 5182-H48 aluminum alloy by using an alkaline degreasing agent, washing by using tap water, then performing acid neutralization, washing by using tap water, washing by using pure water, and finally drying the plate surface by using hot air at 40-60 ℃. The aluminum substrate treated by the procedures can be used for detecting the surface cleanliness by using a dyne pen, and the dyne value of the plate surface is required to be more than or equal to 38dyn/cm before passivation.
(2) Diluting the chromium-free surface treating agent by using deionized water, wherein the weight ratio of the deionized water to the chromium-free surface treating agent is 10: 1, adjusting the pH value to 4-5 by using hydrofluoric acid or ammonia water;
(3) soaking the aluminum substrate with the dyne value of more than or equal to 38dyn/cm for 3-5 seconds, and squeezing out the residual passivation solution on the surface by using a polyurethane rubber roller (soaking and squeezing process);
(4) baking the passivated aluminum substrate in a baking oven at 90 ℃ for 5-8 seconds at the plate temperature of 60-80 ℃ until no obvious liquid residue exists on the surface, wherein the thickness of the passivation film is 5mg/m2～10mg/m 2。
Paint coating:
(1) coating paint in an epoxy acrylic type can cover, coating paint on an RDS #28 wire rod, and curing in an oven after coating the paint, wherein the temperature of a curing plate is 232-241 ℃;
(2) coating paint on an epoxy acrylic type can cover and a pull ring by using a coating material of an RDS #8 wire rod, and curing in an oven after coating the paint, wherein the temperature of a curing plate is 241-249 ℃;
TABLE 2 Performance test
Example 2
A chromium-free surface treatment agent for an aluminum can lid packaging material comprises the following components in parts by mass as shown in the following table 3:
TABLE 3
The chrome-free surface treating agent was prepared by referring to example 1, except that the components used were as shown in table 3, and when the water-soluble silicone-modified resin was added, a water-soluble silicone-modified acrylic resin (viscosity [ rotor viscometer test ]20000cps) solution and a water-soluble silicone-modified urethane resin (self-drying type) solution were added in this order, and the total addition time was not changed; when the chelating agent is added, the maleic acid-acrylic acid copolymer and the hydrolyzed polymaleic anhydride are sequentially added, and the total adding time is not changed.
The passivation step comprises:
(1) aluminum substrate passivation pretreatment: degreasing and deoiling 0.28mm thick 5052-H19 aluminum alloy by using an alkaline degreasing agent, washing with tap water, performing acid neutralization, washing with tap water, washing with pure water, and finally drying the plate surface by using hot air at 40-60 ℃. The aluminum substrate treated by the procedures can be used for detecting the surface cleanliness by using a dyne pen, and the dyne value of the plate surface is required to be more than or equal to 38dyn/cm before passivation.
(2) Diluting the chromium-free surface treating agent by using deionized water, wherein the weight ratio of the deionized water to the chromium-free surface treating agent is 5: 1, adjusting the pH value to 4-5 by using hydrofluoric acid or ammonia water;
(3) spraying the passivation solution to an aluminum substrate with a dyne value of more than or equal to 38dyn/cm for 2-3 seconds by using a 0.2MPa spraying device, and squeezing the residual passivation solution on the surface by using a polyurethane rubber roller (a spraying squeezing process);
(4) baking the passivated aluminum substrate in a baking oven at 90 ℃ for 5-8 seconds at the plate temperature of 60-80 ℃ until no obvious liquid residue exists on the surface, wherein the thickness of the passivation film is 5mg/m2～10mg/m 2。
Paint coating:
(1) coating paint in a vinyl resin can cover, coating the paint by using an RDS #28 wire bar, and curing in an oven after coating the paint, wherein the temperature of a curing plate is 232-241 ℃;
(2) coating paint on the outer surface of a vinyl resin can cover and a pull ring by using a RDS #8 wire rod, and curing in an oven after coating the paint, wherein the temperature of a curing plate is 241-249 ℃.
TABLE 4 Performance test
Example 3
A chromium-free surface treatment agent for an aluminum can lid packaging material comprises the following components in parts by mass as shown in the following table 5:
TABLE 5
Preparation method of chromium-free surface treating agent referring to example 1, except that the components used were as shown in Table 5, and when the azacyclosilane was added, 5-ethyl-4, 6, 11-trioxa-1-aza-5-silabicyclo [3.3.3] undecane, 2-diethoxy-1- (trimethylsilyl) -1-aza-2-silacyclopentane were added in this order; when the water-soluble organic silicon modified resin is added, the water-soluble organic silicon modified epoxy resin solution and the water-soluble organic silicon modified polyurethane resin (self-drying type) solution are sequentially added, and the total adding time is unchanged.
The passivation step comprises:
(1) aluminum substrate passivation pretreatment: degreasing and deoiling 0.26 mm-thick 5182-H39 aluminum alloy by using an alkaline degreasing agent, washing by using tap water, then performing acid neutralization, washing by using tap water, washing by using pure water, and finally drying the plate surface by using hot air at 40-60 ℃. The aluminum substrate treated by the procedures can be used for detecting the surface cleanliness by using a dyne pen, and the dyne value of the plate surface is required to be more than or equal to 38dyn/cm before passivation.
(2) Diluting the chromium-free surface treating agent by using deionized water, wherein the weight ratio of the deionized water to the chromium-free surface treating agent is 10: 1, adjusting the pH value to 4-5 by using hydrofluoric acid or ammonia water;
(3) uniformly coating the passivation solution on an aluminum substrate with a dyne value of more than or equal to 38dyn/cm for 2-3 seconds by using an RDS #3 wire bar (roll coating process);
(4)baking the passivated aluminum substrate in a baking oven at 90 ℃ for 5-8 seconds at the plate temperature of 60-80 ℃ until no obvious liquid residue is left on the surface to obtain a film with the thickness of 5mg/m2～10mg/m 2。
Paint coating:
(1) coating paint in an epoxy acrylic type can cover, coating paint on an RDS #28 wire rod, and curing in an oven after coating the paint, wherein the temperature of a curing plate is 232-241 ℃;
(2) the epoxy acrylic type coating for the outer coating of the can cover and the pull ring is used, the RDS #8 wire rod is used for coating the paint, the paint is coated and then cured in an oven, and the temperature of a curing plate is 241-249 ℃.
TABLE 6 Performance test
Composite membrane of organic-inorganic hybrid architecture: the organic vanadyl carboxylate has a promoting effect on inorganic film formation and organic film formation in passivation, so that a formed passivation non-double-layer passivation film (a first layer is an inorganic oxide film and a second layer is an organic film consisting of resin silane) forms a base on the surface of an aluminum substrate by titanium and silane polymers, and a structure of mixing organic matters and inorganic matters of nano-scale titanium phosphate and resin is combined, so that the structural bonding force is more compact than that of a double-layer passivation film structure, and the bonding force is more stable.
Surface structure of the passivation film: when organic components are low, a dense dentate structure can be formed on a microstructure of the surface of the passivation film, the dentate structure contains polar groups (silane, functional groups of resin, phosphate radicals and the like), paint permeates into the dentate structure after being coated, is dried and thermally cured to form a dropping anchor effect with the dentate structure, and meanwhile, the paint can be combined with the polar groups of the resin and the silane on the dentate structure, so that the adhesive force between the paint and a base material and a coating is improved through physical adhesion and chemical adhesion. Therefore, the structure has excellent coating adhesion, and the close combination with the paint coating can greatly improve the coating performance.
The advantages of the invention include:
1. environmental protection property: heavy metal components such as chromium and the like are not contained, the ROHS instruction requirement is met, water washing is not needed after passivation, and waste water discharge is reduced;
2. low corrosion to aluminum materials: the passivating agent is low in fluorine content, the pH value is controlled to be 4.0-5.0, the corrosion to the aluminum material is further reduced, and the aluminum loss is reduced in the passivating process;
3. passivating the anti-flocculent precipitate: the surface treating agent has low corrosivity on an aluminum substrate, can reduce aluminum alloy components dissolved in passivation to form flocculent precipitates, avoids using components (such as sulfate radical-containing substances and the like) which are easy to react with metal ions in the aluminum alloy to generate precipitates in passivation, plays a role in preventing flocculent precipitates for a small amount of aluminum alloy ions dissolved in passivation through the action of a chelating agent, and plays a role in preventing the flocculent precipitates through the comprehensive effect of the performances.
4. The passivation service life is long, the groove replacement period is long: based on the passivation treatment, the aluminum substrate has low corrosion resistance, flocculent precipitates can be effectively prevented from appearing, the passivation can be continuously used for a long time, and the passivation tank liquid does not need to be frequently drained and replaced by new tank liquid.
5. The colorless and transparent passivation film does not produce color difference on the surface of the passivated aluminum plate: the reasons for the color difference of the aluminum plate surface are as follows: (1) the passivation film is colored, and the thickness of the passivation film on the aluminum plate surface is uneven, so that color difference is easy to form; (2) when the passivation solution is coated on the surface of the plate unevenly, the surface of the plate is easy to have a color difference phenomenon; (3) the surface treatment agent contains substances with strong oxidizability (such as nitrate ions and the like), and the passivation solution is easy to have color difference when the plate surface is unevenly coated (cannot be seen under the normal temperature condition, and is easy to appear in high-temperature cooking and acid cooking tests). The passivation film formed by the invention is colorless and transparent, has low fluorine ion content and weak acidity in the components, contains slow-release components such as organic carboxylic acid vanadyl complex, chelating agent and the like, does not contain substances with strong oxidizing property, and is not easy to generate color difference.
6. The passivation treatment speed is high (the passivation treatment time is 1-5 seconds), the drying temperature is low (the film can be formed at the plate temperature PMT of 60-80 ℃), the energy consumption is saved, and the method is suitable for a production line for continuous treatment.
The technical solutions provided by the embodiments of the present invention are described in detail above, and the principles and embodiments of the present invention are explained herein by using specific examples, and the descriptions of the embodiments are only used to help understanding the principles of the embodiments of the present invention; meanwhile, for a person skilled in the art, according to the embodiments of the present invention, there may be variations in the specific implementation manners and application ranges, and in summary, the content of the present description should not be construed as a limitation to the present invention.
Claims (10)
1. A chromium-free surface treating agent for an aluminum can lid packaging material is characterized in that:
the coating comprises the following components in percentage by mass:
2. the chromium-free surface treatment agent for aluminum can lid packaging material according to claim 1, characterized in that:
the azacyclo-silane is one or more than two of 5-ethyl-4, 6, 11-trioxa-1-aza-5-silabicyclo [3.3.3] undecane, N-N-butyl-aza-2, 2-dimethoxy silacyclopentane, 2-diethoxy-1- (trimethylsilyl) -1-aza-2-silacyclopentane and 2, 2-dimethoxy-1, 6-diaza-2-silacyclooctane.
3. The chromium-free surface treatment agent for aluminum can lid packaging material according to claim 1 or 2, characterized in that:
the water-soluble organic silicon modified resin is one or more of water-soluble organic silicon acrylic acid modified resin, water-soluble organic silicon modified epoxy resin and water-soluble organic silicon modified polyurethane resin.
4. The chromium-free surface treatment agent for aluminum can lid packaging material according to claim 1, characterized in that:
the chelating agent is one or more of low molecular polyacrylic acid, maleic acid-acrylic acid copolymer and hydrolyzed polymaleic anhydride.
5. The chromium-free surface treatment agent for aluminum can lid packaging material according to claim 1, characterized in that:
the organic carboxylic acid vanadyl complex is one or two of vanadyl oxalate and vanadyl acetylacetonate.
6. A method for preparing a chromium-free surface treatment agent for aluminum can lid packaging materials according to any one of claims 1 to 5, characterized in that:
the method comprises the following steps:
(1) dissolving ammonium fluotitanate in water to prepare an ammonium fluotitanate solution for later use; dissolving ammonium phosphate in pure water to prepare ammonium phosphate solution;
(2) slowly adding an ammonium fluotitanate solution into the ammonium phosphate solution while dispersing, and uniformly dispersing to prepare a fluorine-containing titanium phosphate solution;
(3) adding propylene glycol propyl ether into the fluorine-containing titanium phosphate solution, and uniformly dispersing;
(4) cooling the solution prepared in the step (3), and adding azacyclo-silane while dispersing;
(5) dissolving water-soluble organic silicon modified resin in water to obtain an organic silicon modified resin solution, and adding the organic silicon modified resin solution into the liquid in the step (4) while dispersing;
(6) dissolving an organic carboxylic acid vanadyl complex in water to obtain an organic carboxylic acid vanadyl complex solution, adding the organic carboxylic acid vanadyl complex solution into the solution obtained in the step (5), and uniformly dispersing;
(7) and (4) slowly adding a chelating agent into the solution obtained in the step (6), and uniformly dispersing to obtain the chromium-free surface treating agent.
7. The method for preparing a chromium-free surface treatment agent for an aluminum can lid packaging material according to claim 6, characterized in that:
and (3) in the step (2), the dispersion speed is 800-1200 r/min in the process of adding the ammonium fluotitanate solution, the solution is gradually changed into white emulsion, and the solution is continuously dispersed for 20-30 minutes at the rotating speed of 300-500 r/min after the addition.
8. The method for preparing a chromium-free surface treatment agent for an aluminum can lid packaging material according to claim 6, characterized in that:
and (4) cooling the solution to 10-15 ℃, adding azacyclo-silane by using a metering pump according to the adding time of 3 hours, and dispersing at the speed of 800-1200 r/min while adding azacyclo-silane.
9. The method for preparing a chromium-free surface treatment agent for an aluminum can lid packaging material according to claim 6, characterized in that:
the weight ratio of the water-soluble organic silicon modified resin to the water in the step (5) is 30-50: 100, adding the organic silicon modified resin solution into the liquid in the step (4) by using a metering pump according to the adding time of 30 minutes, adding the organic silicon modified resin solution, dispersing at the speed of 800-1200 r/min, and continuing to disperse for 15 minutes after the adding is finished;
in the step (6), the weight ratio of the organic carboxylic acid vanadyl complex to the water is 3: and (100) adding the organic carboxylic acid vanadyl complex solution into the liquid in the step (5) by using a metering pump according to the addition time of 30 minutes, and continuing to disperse for 15 minutes after the addition is finished.
10. A passivation process using the chromium-free surface treatment agent for aluminum can lid packaging material according to any one of claims 1 to 9, characterized in that:
the method comprises the following steps:
(1) passivating and pretreating an aluminum substrate;
(2) diluting the chromium-free surface treating agent by using deionized water, wherein the weight ratio of the deionized water to the chromium-free surface treating agent is 5-10: 1, adjusting the pH value to 4-5 by using hydrofluoric acid or ammonia water;
(3) passivating the aluminum substrate by a roller coating or soaking squeezing or spraying squeezing process, wherein the treatment time of the chromium-free surface treating agent is 1-5 seconds;
(4) and baking the passivated aluminum substrate in a baking oven at 90 ℃ for 5-8 seconds until no obvious liquid residue exists on the surface, wherein the temperature of the plate reaches 60-80 ℃.
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