CN105925970A - Surface treatment agent used before metal material cathode electrophoresis coating - Google Patents
Surface treatment agent used before metal material cathode electrophoresis coating Download PDFInfo
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- CN105925970A CN105925970A CN201610551816.2A CN201610551816A CN105925970A CN 105925970 A CN105925970 A CN 105925970A CN 201610551816 A CN201610551816 A CN 201610551816A CN 105925970 A CN105925970 A CN 105925970A
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- Prior art keywords
- metal material
- processing agent
- list processing
- coating
- before metal
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- 239000007769 metal material Substances 0.000 title claims abstract description 45
- 238000001962 electrophoresis Methods 0.000 title abstract description 12
- 239000011248 coating agent Substances 0.000 title abstract description 7
- 238000000576 coating method Methods 0.000 title abstract description 6
- 239000012756 surface treatment agent Substances 0.000 title abstract 4
- 239000002105 nanoparticle Substances 0.000 claims abstract description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 7
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 7
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 7
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229960001763 zinc sulfate Drugs 0.000 claims abstract description 7
- 229910000368 zinc sulfate Inorganic materials 0.000 claims abstract description 7
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims abstract description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 6
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims abstract description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 3
- 238000012545 processing Methods 0.000 claims description 42
- 239000003795 chemical substances by application Substances 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 28
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 25
- 238000004070 electrodeposition Methods 0.000 claims description 19
- -1 siloxanes Chemical class 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 235000013305 food Nutrition 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000001117 sulphuric acid Substances 0.000 claims description 3
- 235000011149 sulphuric acid Nutrition 0.000 claims description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 159000000007 calcium salts Chemical group 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- 150000002696 manganese Chemical class 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 239000013638 trimer Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims 1
- 150000002927 oxygen compounds Chemical class 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 13
- 239000002184 metal Substances 0.000 abstract description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract 2
- 125000003277 amino group Chemical group 0.000 abstract 2
- 230000008569 process Effects 0.000 description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 229910052742 iron Inorganic materials 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- DZGCGKFAPXFTNM-UHFFFAOYSA-N ethanol;hydron;chloride Chemical compound Cl.CCO DZGCGKFAPXFTNM-UHFFFAOYSA-N 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 7
- 238000004448 titration Methods 0.000 description 7
- 238000011010 flushing procedure Methods 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 5
- 238000003556 assay Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229960004756 ethanol Drugs 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000012086 standard solution Substances 0.000 description 4
- 235000013339 cereals Nutrition 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000009182 swimming Effects 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 150000003755 zirconium compounds Chemical class 0.000 description 2
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000001792 White test Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229940091250 magnesium supplement Drugs 0.000 description 1
- CCERQOYLJJULMD-UHFFFAOYSA-M magnesium;carbanide;chloride Chemical compound [CH3-].[Mg+2].[Cl-] CCERQOYLJJULMD-UHFFFAOYSA-M 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000001507 sample dispersion Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 150000003601 thymols Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium(II) oxide Chemical compound [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 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
-
- 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
- C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/20—Pretreatment
Abstract
The invention discloses a surface treatment agent used before metal material cathode electrophoresis coating. Every liter of the surface treatment agent comprises 80-150mg of water-soluble oligosiloxane, 50mg of zirconyl nitrate, 100mg of titanyl sulfate, 100mg of aluminum nitrate and/or zinc sulfate, 70-80mg of lithium carbonate, 100-120mg of hydrofluoric acid, 80-100mg of oxide nanoparticles with the surface grafted with an amino group and/or a hydroxyl group, 100-150mg of ethanol, 50-100mg of polyethylene glycol with the molecular weight of 300-600, 1-5mg of ferrous sulfate, and the balance of water, wherein the grafting amount of the hydroxyl group on the surface of the oxide nanoparticles is 1.4-5mmol/g, and the grafting amount of the amino group on the surface of the oxide nanoparticles is 0.9-5mmol/g. The surface treatment agent greatly improves the resistance of the metal surface.
Description
Technical field
The present invention relates to a kind of list processing agent before metal material cathode electro-coating, belong to industrial media technology neck
Territory.
Background technology
Metal material typically requires before carrying out application and carries out surface process to strengthen the adhesion property between metal and coating, mesh
Before, the metal surface treatment technology many employings phosphorization treatment process before application.But, this processing method is owing to having containing zinc, nickel etc.
The evil chemical composition such as heavy metal ion and phosphorus, and production produces substantial amounts of phosphatization slag, environment can be caused potentially hazardous.
Meanwhile, phosphorization treatment technology power consumption is relatively big, adjusts technique degree of dependence big in the table in front road, and this also can increase the difficulty of cost and management
Degree.
As the technology that can substitute conventional phosphatizing processing mode, it is known that have Zirconium compound or Zirconium compound combine
Organosilan processing mode.But the metal material surface chemical reaction film layer that existing non-phosphatization processing mode obtains is thin, film layer
Sparse the finest and close, thus cause metal material surface resistance low, for having relatively in car body and parts, or other industry
For the metal material of labyrinth, it is accordingly required in particular to form fine and close thick and heavy chemical composition coating layer at metal material surface, enter
And improve metal surface resistance, so that metal material is when follow-up cathode electro-coating, electrophoretic coating has high throwing power.
The exploitation of a kind of non-phosphatization list processing agent that can be effectively improved metal surface resistance value is necessary.
Summary of the invention
The technical problem to be solved is to provide a kind of list processing before metal material cathode electro-coating
Agent, this list processing agent can be greatly improved the resistance value of metal surface.
For solving above-mentioned technical problem, the technical solution adopted in the present invention is:
A kind of list processing agent before metal material cathode electro-coating, in every L list processing agent, by the group of following quality
It is grouped into: 80～150mg water soluble oligomer siloxanes, 50mg zirconyl nitrate or fluorine zirconic acid, 100mg titanyl sulfate or fluotitanic acid,
100mg aluminum nitrate and/or zinc sulfate, 70～80mg lithium carbonate or potassium hydroxide or Ammonium bicarbonate food grade, 100～120mg Fluohydric acid. or
Nitric acid or sulphuric acid, 80～100mg surface grafting have amino and/or the oxide nano particles of hydroxyl, 100～150mg ethanol, 50
～Polyethylene Glycol, 1～5mg ferrous sulfate that 100mg molecular weight is 300～600 and water surplus；Wherein, described oxide is received
The grafting amount of rice grain surface hydroxyl is 1.4～5mmol/g, and the grafting amount of described oxide nanoparticle surface amino is 0.9
～5mmol/g, the ratio of described oxide nanoparticle surface hydroxyl and amino grafting amount is 0.3～4.1.
Further preferably, described water soluble oligomer siloxanes is trimer siloxanes, tetramer siloxanes, pentamer silica
Alkane or six aggressiveness siloxanes.
Further preferably, described oxide nano particles is nano SiO 2 particle and/or titania nanoparticles
And/or zirconium dioxide nanoparticles.
Further preferably, the particle diameter of described nano SiO 2 particle is 5～10nm；Described titania nanoparticles
Particle diameter is 6～8nm；The particle diameter of described zirconium dioxide nanoparticles is 5～6nm, and oxide nano particles is under such particle diameter
Easily dispersion, is difficult to reunite, the stability of advantageously combined objects system, and is of value to compositions and deposits film forming in metal surface.
Further preferably, described aluminum nitrate or zinc sulfate can also be substituted by the calcium salt of equivalent, manganese salt or iron salt.
Further preferably, the pH value of described list processing agent is 4～5.
Further preferably, described surface grafting has the oxide nano particles of amino and/or hydroxyl to adopt to make with the following method
For forming: the oxide nano particles that a certain amount of particle diameter is 5～10nm is placed in ethanol, isopropanol or toluene solvant；Again
The desired amount of γ-aminopropyltrimethoxysilane and/or gamma-aminopropyl-triethoxy-silane, described γ-ammonia is added in solvent
The addition of propyl trimethoxy silicane and/or gamma-aminopropyl-triethoxy-silane is the 1% of oxide nano particles addition
～1.5%；By mixed material in rotating speed be 1000～1500r/min down cuts 50～60min；By the suspension that obtains in 40～
Agitating heating 12～24h at 60 DEG C, more scrubbed, filter and dried i.e. can get the oxidation of amino and/or hydroxyl modification
Thing nano-particle.Containing of control oxide nano grain surface hydroxyl and amino is carried out by controlling the addition of silane coupler
Amount, the content ratio of oxide nanoparticle surface hydroxyl and amino just both must can make product in the range of the present invention is limited
The film layer of dense regular can be formed at metal material surface, enhancing metal material can also be played simultaneously and adhere to follow-up electrophoretic coating
The effect of power.
The method measuring oxide nanoparticle surface hydroxy radical content: to taking out equipped with modified oxide nano particles
Filter flask adds dry toluene, with dispersal oxide nano-particle；The pipeline of titration appratus is dried, and in bottle,suction
Rapidly join the methyl-magnesium-chloride being stored in constant pressure funnel, use drainage eudiometer to collect the gas V1 generated,
Until reaction is completely；Blank assay: measure the gas flow V2 generated when being added without modified oxide nano particles, as the following formula
The content of calculating oxide nanoparticle surface hydroxyl:
In formula: COHFor oxide nanoparticle surface hydroxy radical content, unit is mmol/g；P is atmospheric pressure, and unit is
Pa；V1 generates gas volume for experiment, and unit is m3；V2 is that blank assay generates gas volume, and unit is m3；M is sample matter
Amount, unit is g；T is experimental temperature, and unit is K；R is gas constant, and unit is (m3·Pa)/(K·mol)。
The method measuring oxide nanoparticle surface amino content: by a certain amount of modified oxide nano particles,
Join in 100ml dehydrated alcohol or isopropanol, ultrasonic 10min, until sample dispersion all with after, add 5～10 thymols
Blue indicator solution, with hydrochloric acid-ethanol standard solution titration, solution colour is titration end-point from the faint yellow pink that becomes, with
Shi Jinhang blank assay；Blank assay: carry out in the case of being added without modified oxide nano particles.The most according to the following formula
Computing function nano-oxide particle surface amino content:
In formula:For oxide nanoparticle surface amino content, unit is mmol/g；C is that hydrochloric acid-ethanol solution rubs
That concentration, unit is mol/L；V5 is the volume consuming hydrochloric acid-ethanol solution in EXPERIMENTALTitration, and unit is mL；V6 is blank real
Testing the volume of consumption hydrochloric acid-ethanol solution, unit is mL.
Hydrochloric acid-ethanol standard solution forming steps is as follows: 1. measure the concentrated hydrochloric acid that 9ml mass concentration is 36%, adds nothing
Water-ethanol is diluted to 1000ml, mix homogeneously and get final product；2. it is taken at 270-300 DEG C and is dried the benchmark natrium carbonicum calcinatum 0.1g to constant weight
It is placed in conical flask, after adding 50ml deionized water dissolving, adds C.I. 13020 .-bromocresol green mixed indicator 10, with above-mentioned
Hydrochloric acid-ethanol solution be titrated to solution colour by green transition be kermesinus be titration end-point, carry out blank assay simultaneously；3. empty
White test: carry out in the case of being added without sodium carbonate.It is calculated as follows the molar concentration of hydrochloric acid-ethanol solution:
In formula: the actual concentrations of c-hydrochloric acid-ethanol standard titration solution, unit is mol/L；M-benchmark natrium carbonicum calcinatum
Quality, unit is g；In V3-experiment, titration consumes hydrochloric acid-ethanol standard solution volume, and unit is mL；V4-blank experiment drips
Surely consuming hydrochloric acid-ethanol standard solution volume, unit is mL；0.0530 for (concentration is with 1.00mL Hydrochloric Standard Titration
The quality of 1mol/L) suitable benchmark natrium carbonicum calcinatum, unit is g.
Compared to prior art, technical solution of the present invention has the beneficial effect that
The advantage that list processing agent of the present invention has good stability, wettability is good, and the metal material after processing can direct water
Wash (illustrating that product of the present invention is strong at metal surface adhesive force, be difficult to come off from metal material surface)；Inventive formulation uses poly-
Siloxanes substitutes monomeric silanes coupling agent, effectively enhances the stability of system, due to monomeric silanes coupling agent difficulty in system
With dispersion, easily assemble agglomerating, thus have impact on performance and the stability of system；It addition, inventive formulation uses is grafted with amino
And/or the oxide nano particles of hydroxyl, surface has the oxide nano particles of functional group and shows attachment at metal material
Power is strong, is difficult to come off from metal material surface, and follow-up electrophoresis film and the adhesive force of metal material；The present invention joins
Product can be made to get off in the calmness that metal material surface is orderly, form the film layer of dense regular, thus improve metal material table
The resistance value in face, the resistance value of the metal material surface after using the present invention non-phosphatization list processing agent to process can reach 1.5～2.5
Ohm/every square centimeter, 0.2～0.5 ohm/every square centimeter of the most existing non-phosphatization list processing agent, therefore gold
Genus material is when follow-up cathode electro-coating, and electrophoretic coating has high throwing power, and inventive formulation can also improve metal material
What surface and follow-up electrophoresis process were formed is coated with intermembranous adhesive force.
Accompanying drawing explanation
Fig. 1 is that after using list processing agent of the present invention to process, metal material shows that the chemical reaction film layer formed is partially schematic
Figure；
Fig. 2 is that after using existing non-phosphatization list processing agent to process, metal material shows that the chemical reaction film layer formed local shows
It is intended to.
Detailed description of the invention
According to following embodiment, the present invention be may be better understood.But, as it will be easily appreciated by one skilled in the art that reality
Execute the content described by example and be merely to illustrate the present invention, and should be also without limitation on basis described in detail in claims
Invention.
List processing agent treated metal material of the present invention, including ferrum and/or its alloy material, zinc and/or its alloy material
Material, aluminum and/or its alloy material and magnesium and/or its alloy material.
Water soluble oligomer siloxanes employed in list processing agent prescription of the present invention is:
Dynasylan the Hydrosil 2926 and/or Dynasylan Hydrosil 2776 of Dehussa company.
Embodiment 1
Present invention list processing agent before metal material cathode electro-coating, in every L list processing agent, by following quality
Component forms: 100mg water soluble oligomer siloxanes (Dynasylan Hydrosil 2926), 50mg zirconyl nitrate, 100mg sulfur
Acid oxygen titanium, 100mg aluminum nitrate, 70mgLi2CO3, 100mg sulphuric acid, 80mg surface grafting have the oxidate nano of amino and hydroxyl
Grain, 100mg ethanol, 50mg molecular weight are the Polyethylene Glycol of 600, (ferrous sulfate can strengthen the reaction of system to 2mg ferrous sulfate
Activity, promotes the generation of reaction and improves reaction efficiency) and water surplus；Wherein, described oxide nanoparticle surface hydroxyl
Grafting amount be 5mmol/g, the grafting amount of described oxide nanoparticle surface amino is 5mmol/g, oxide nano particles
The ratio of surface hydroxyl and amino grafting amount is 1.
The pH value of present invention list processing agent before metal material cathode electro-coating is 5.
Embodiment 2
Present invention list processing agent before metal material cathode electro-coating, in every L list processing agent, by following quality
Component forms: 80mg water soluble oligomer siloxanes (Dynasylan Hydrosil 2926), 70mg water soluble oligomer siloxanes
(Dynasylan Hydrosil 2776), 50mg fluorine zirconic acid, 100mg titanyl sulfate, 50mg aluminum nitrate, 50mg zinc sulfate, 70mg
Potassium hydroxide, 100mg nitric acid, 100mg surface grafting have amino and the oxide nano particles of hydroxyl, 120mg ethanol, 80mg to divide
Son amount is Polyethylene Glycol, 3mg ferrous sulfate and the water surplus of 600；Wherein, the connecing of described oxide nanoparticle surface hydroxyl
Branch amount is 1.4mmol/g, and the grafting amount of described oxide nanoparticle surface amino is 3.8mmol/g, oxide nano particles
The ratio of surface hydroxyl and amino grafting amount is 0.37.
The pH value of present invention list processing agent before metal material cathode electro-coating is 4.5.
Embodiment 3
Present invention list processing agent before metal material cathode electro-coating, in every L list processing agent, by following quality
Component forms: 50mg water soluble oligomer siloxanes (Dynasylan Hydrosil 2926), 100mg water soluble oligomer siloxanes
(Dynasylan Hydrosil 2776), 50mg fluorine zirconic acid, 100mg fluotitanic acid, 100mg zinc sulfate, 80mg Ammonium bicarbonate food grade,
120mg Fluohydric acid., 100mg surface grafting have amino and the oxide nano particles of hydroxyl, 150mg ethanol, the 100mg molecular weight to be
Polyethylene Glycol, 5mg ferrous sulfate and the water surplus of 600；Wherein, the grafting amount of described oxide nanoparticle surface hydroxyl is
3.7mmol/g, the grafting amount of described oxide nanoparticle surface amino is 0.9mmol/g, oxide nanoparticle surface hydroxyl
The ratio of base and amino grafting amount is 4.1.
The pH value of present invention list processing agent before metal material cathode electro-coating is 4.2.
Embodiment 4
Using commercially available Q235 cold-rolled steel sheet (species abundance in Baosteel in Shanghai production), specification is made for (170mm × 100mm × 0.8mm)
Set-iron for the present embodiment.
First metal sample is carried out the degreasing cleaning process that metal material shows；Then set-iron is placed in embodiment
Soaking 5 minutes in the list processing agent of 1, immediately process with water flushing after immersion, the resistance value on the set-iron surface after process is
1.5 ohm/every square centimeter, after flushing, set-iron is in the case of moistened surface, uses cathode electrophoresis dope HD8000 (to close
Western company manufactures) carry out ability cathode electrophoresis process, the model after electrophoretic process uses deionized water rinsing 30 seconds.After washing
After electrophoresis, model is dried 20 minutes under the conditions of 180 DEG C, takes out room temperature and dries its film thickness of detection in 20 μm ± 1 μ m
Obtaining test piece, test piece specifically detects performance and is shown in Table 1.
Embodiment 5
Using commercially available galvanized steel plain sheet, specification is the metal-like that (170mm × 100mm × 0.8mm) is used as the present embodiment
Plate.
First metal sample is carried out the degreasing cleaning process that metal material shows；Then set-iron is placed in embodiment
Soaking 2 minutes in the list processing agent of 2, immediately process with water flushing after immersion, the resistance value on the set-iron surface after process is
2.0 ohm/every square centimeter, after flushing, set-iron is in the case of moistened surface, uses cathode electrophoresis dope ECO3000
(manufacture of KCC company) carries out ability cathode electrophoresis process, and the model after electrophoretic process uses deionized water rinsing 30 seconds.After washing
Electrophoresis after model under the conditions of 180 DEG C be dried 20 minutes, take out room temperature dry detection its film thickness at 20 μm ± 1 μ m
The most i.e. obtaining test piece, test piece specifically detects performance and is shown in Table 1.
Embodiment 6
Using commercially available aluminium sheet, specification is the set-iron that (170mm × 100mm × 0.8mm) is used as the present embodiment.
First metal sample is carried out the degreasing cleaning process that metal material shows；Then set-iron is placed in embodiment
Soaking 8 minutes in the list processing agent of 3, immediately process with water flushing after immersion, the resistance value on the set-iron surface after process is
2.5 ohm/every square centimeter, after flushing, set-iron is in the case of moistened surface, uses cathode electrophoresis dope ED6C (PPG
Company manufactures) carry out ability cathode electrophoresis process, the model after electrophoretic process uses deionized water rinsing 30 seconds.By the electricity after washing
After swimming, model is dried 20 minutes under the conditions of 180 DEG C, and taking-up room temperature is dried its film thickness of detection and in 20 μm ± 1 μ m is
Obtaining test piece, test piece specifically detects performance and is shown in Table 1.
Table 1
As shown in Fig. 1～2, the precipitation that list processing agent of the present invention can be orderly in metal surface, the chemical reaction film obtained
Layer dense regular, thus cause metal material surface resistance value high, and oxide nano particles is at metal material surface adhesive force
By force, difficult drop-off, and the film layer arrangement that existing list processing agent obtains is loose, thus cause metal material surface resistance value low.
List processing agent stability of the present invention is high, wettability is good, and after process, the chemical reaction film layer of metal surface gained has
The advantage that film thickness, resistance value are high and corrosion resistance is strong, significantly improves the throwing power in follow-up electrophoretic painting, and with follow-up electricity
The adhesion of the film that swimming technique is formed is the strongest.
Claims (7)
1. the list processing agent before metal material cathode electro-coating, it is characterised in that: in every L list processing agent, by such as
The component composition of lower quality: 80～150mg water soluble oligomer siloxanes, 50mg zirconyl nitrate or fluorine zirconic acid, 100mg titanyl sulfate
Or fluotitanic acid, 100mg aluminum nitrate and/or zinc sulfate, 70～80mg lithium carbonate or potassium hydroxide or Ammonium bicarbonate food grade, 100～120mg
Fluohydric acid. or nitric acid or sulphuric acid, 80～100mg surface grafting have amino and/or the oxide nano particles of hydroxyl, 100～
150mg ethanol, 50～Polyethylene Glycol, 1～5mg ferrous sulfate that 100mg molecular weight is 300～600 and water surplus；Wherein,
The grafting amount of described oxide nanoparticle surface hydroxyl is 1.4～5mmol/g, described oxide nanoparticle surface amino
Grafting amount is 0.9～5mmol/g, and the ratio of described oxide nanoparticle surface hydroxyl and amino grafting amount is 0.3～4.1.
List processing agent before metal material cathode electro-coating the most according to claim 1, it is characterised in that: described water
Dissolubility oligosiloxane is trimer siloxanes, tetramer siloxanes, pentamer siloxanes or six aggressiveness siloxanes.
List processing agent before metal material cathode electro-coating the most according to claim 1, it is characterised in that: described oxygen
Compound nano-particle is nano SiO 2 particle and/or titania nanoparticles and/or zirconium dioxide nanoparticles.
List processing agent before metal material cathode electro-coating the most according to claim 3, it is characterised in that: described two
The particle diameter of silicon oxide nano-particle is 5～10nm；The particle diameter of described titania nanoparticles is 6～8nm；Described zirconium dioxide
The particle diameter of nano-particle is 5～6nm.
List processing agent before metal material cathode electro-coating the most according to claim 1, it is characterised in that: described nitre
Acid aluminum or zinc sulfate can also be substituted by the calcium salt of equivalent, manganese salt or iron salt.
List processing agent before metal material cathode electro-coating the most according to claim 1, it is characterised in that: described table
The pH value of inorganic agent is 4～5.
List processing agent before metal material cathode electro-coating the most according to claim 1, it is characterised in that: described table
Face is grafted with the oxide nano particles of amino and/or hydroxyl and adopts and be prepared from the following method: by a certain amount of particle diameter be 5～
The oxide nano particles of 10nm is placed in ethanol, isopropanol or toluene solvant；The desired amount of γ-ammonia third is added again in solvent
Base trimethoxy silane and/or gamma-aminopropyl-triethoxy-silane, described γ-aminopropyltrimethoxysilane and/or γ-ammonia
The addition of propyl-triethoxysilicane is the 1%～1.5% of oxide nano particles addition；By mixed material in rotating speed it is
1000～1500r/min down cuts 50～60min；Suspension agitating heating 12～24h at 40～60 DEG C that will obtain, then warp
Washing, filtration and dried i.e. can get the oxide nano particles of amino and/or hydroxyl modification.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107587126A (en) * | 2017-07-19 | 2018-01-16 | 合肥普庆新材料科技有限公司 | A kind of nano ceramics silane complex film layer transforming agent containing graphene oxide |
| CN109423683A (en) * | 2017-08-30 | 2019-03-05 | 广东新会中集特种运输设备有限公司 | The finishing system of container and the coating process of container |
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| CN109423683A (en) * | 2017-08-30 | 2019-03-05 | 广东新会中集特种运输设备有限公司 | The finishing system of container and the coating process of container |
| CN109423683B (en) * | 2017-08-30 | 2021-03-23 | 广东新会中集特种运输设备有限公司 | Container coating system and container coating method |
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