CN114921778A - Environment-friendly coating pretreatment liquid and preparation method and application thereof - Google Patents
Environment-friendly coating pretreatment liquid and preparation method and application thereof Download PDFInfo
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- CN114921778A CN114921778A CN202210521589.4A CN202210521589A CN114921778A CN 114921778 A CN114921778 A CN 114921778A CN 202210521589 A CN202210521589 A CN 202210521589A CN 114921778 A CN114921778 A CN 114921778A
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- 239000011248 coating agent Substances 0.000 title claims abstract description 61
- 238000000576 coating method Methods 0.000 title claims abstract description 61
- 239000007788 liquid Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229920005989 resin Polymers 0.000 claims abstract description 32
- 239000011347 resin Substances 0.000 claims abstract description 32
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 28
- 230000002378 acidificating effect Effects 0.000 claims abstract description 25
- 239000008213 purified water Substances 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 13
- 238000011282 treatment Methods 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 15
- 229920002635 polyurethane Polymers 0.000 claims description 14
- 239000004814 polyurethane Substances 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000003002 pH adjusting agent Substances 0.000 claims description 6
- 238000007747 plating Methods 0.000 claims description 5
- 238000005238 degreasing Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims 1
- 239000011707 mineral Substances 0.000 claims 1
- 239000002480 mineral oil Substances 0.000 claims 1
- 235000010446 mineral oil Nutrition 0.000 claims 1
- 239000004094 surface-active agent Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 12
- 239000002184 metal Substances 0.000 abstract description 12
- 239000010410 layer Substances 0.000 abstract description 9
- 239000011247 coating layer Substances 0.000 abstract description 8
- 150000003839 salts Chemical class 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 description 19
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 10
- 230000007797 corrosion Effects 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011572 manganese Substances 0.000 description 7
- 229920006264 polyurethane film Polymers 0.000 description 7
- 239000007921 spray Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- FRHOZLBTKXGMDH-UHFFFAOYSA-N [Zr].[F] Chemical compound [Zr].[F] FRHOZLBTKXGMDH-UHFFFAOYSA-N 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- 238000004017 vitrification Methods 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- -1 rare earth compounds Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to an environment-friendly coating pretreatment liquid, a preparation method and an application thereof, wherein each liter of the coating pretreatment liquid contains: h 2 ZrF 6 ：2.0～4.0g，Mn(NO 3 ) 2 ：2.0～4.0g，Na 2 SO 4 ·10H 2 O: 0.4-0.5 g, acid resin: 0.5 to 1.0g, silica sol: 0.3-0.4 g, KH-550: 1.0-1.2 g, absolute ethyl alcohol: 3.0-6.0 g of pH value regulator and the balance of purified water; the pH value of the environment-friendly coating pretreatment liquid is 2.0-4.0. The environment-friendly coating pretreatment liquid provided by the invention takes the fluorozirconium salt and the acidic resin as main film forming systems, the silica sol and the KH-550 are added to modify the fluorozirconium salt and the acidic resin, hydrophilic coating layer groups are added in the systems, and the film layer can improve the binding force of a subsequent coating layer to a great extent after being deposited on the surface of a metal workpiece through reaction.
Description
Technical Field
The invention relates to the technical field of metal surface treatment, in particular to an environment-friendly coating pretreatment liquid and a preparation method and application thereof.
Background
Before coating, the metal surface needs to be subjected to a plurality of series of pre-treatments, such as degreasing, derusting and other necessary purification processes. Meanwhile, in order to prevent rust and improve coating binding force between processes of exposing the substrate after purification, chemical treatment is often required to form a protective film on the surface of the substrate.
The traditional fluozirconate vitrification agent has simple process and low price and can be widely applied. But the comprehensive performance requirements of long-time rust prevention and higher coating and plating binding force between working procedures cannot be met.
Patent CN104789954A discloses a lubricating type water-based metal surface treatment agent, which contains fluorozirconic acid, gamma-aminopropyltriethoxysilane, manganese nitrate and polyurethane resin, but the patent component also contains environmentally unfriendly phosphorus element, and the phosphorization method has serious phosphorus pollution, which will result in greatly increased wastewater treatment cost. In view of the current increasingly higher environmental requirements, the formula of the composition needs to be further optimized and improved.
Patent CN107012456A discloses a metal surface pretreatment agent modified by alkoxy silane ethyl polyhedral oligomeric silsesquioxane, which takes water as solvent, silane and fluozirconate as film forming agent, and adds alkoxy silane ethyl polyhedral oligomeric silsesquioxane as grinding sealing agent and repairing agent. However, rare earth elements are also used in the patent, the rare earth elements are not only scarce in resources and high in price, but also the rare earth compounds generally need high-precision purification, otherwise, physicochemical property fluctuation is easily caused in mass production and use, and the stability of the product is poor.
Patent CN109321908A discloses a multifunctional environment-friendly nano-ceramic liquid for metal surfaces, which contains fluorozirconic acid, manganese nitrate, nano-silica sol, organic resin and other components, but the aqueous organic resin in the components of the invention is an acrylic resin and organic silicon resin system, the two resins are modified by emulsion to increase more hydrophilic groups so as to obtain better water solubility, and when a large amount of hydrophilic groups and lower molecular weight exist, the corrosion resistance is poorer.
Disclosure of Invention
In view of the above technical deficiencies, an object of the present invention is to provide an environment-friendly pre-coating treatment solution, which can well solve the problems of rust prevention and comprehensive performance of improving the binding force of the coating layer during long-time working procedures.
The technical scheme adopted by the invention is as follows:
an environment-friendly coating pretreatment liquid, wherein each liter of the coating pretreatment liquid contains:
H 2 ZrF 6 ：2.0～4.0g，Mn(NO 3 ) 2 ：2.0～4.0g，Na 2 SO 4 ·10H 2 o: 0.4-0.5 g, acidic resin: 0.5 to 1.0g, silica sol: 0.3-0.4 g, KH-550: 1.0-1.2 g, absolute ethyl alcohol: 3.0 to 6.0g of pH value regulator and the balance of purified water; the pH value of the environment-friendly coating pretreatment liquid is 2.0-4.0.
Preferably, the pH adjuster is a sulfuric acid solution with a mass fraction of 10% or a sodium hydroxide solution with a mass fraction of 10%.
Preferably, the pre-coating treatment liquid contains H per liter 2 ZrF 6 4.0g，Mn(NO 3 ) 2 4.0g， Na 2 SO 4 ·10H 2 0.5g of O, 1.0g of acid resin, 0.4g of silica sol, KH-5501.2 g, 6.0g of absolute ethyl alcohol, a pH value regulator and the balance of purified water.
Preferably, the silica sol has a particle size of 10nm and is SiO 2 Acidic SiO with mass content more than or equal to 30 percent 2 And (3) dispersing the mixture.
Preferably, the acidic resin is aqueous polyurethane.
The second purpose of the invention is to provide a preparation method of the environment-friendly coating pretreatment liquid, which comprises the following steps:
s1, weighing raw materials of each component with required mass and required concentration;
s2, sequentially dissolving KH-550 and ethanol in a certain amount of purified water, and stirring to dissolve until the solution is clear to obtain a front liquid A;
s3, mixing H 2 ZrF 6 、Mn(NO 3 ) 2 And Na 2 SO 4 ·10H 2 Dissolving O in a certain amount of purified water in turn, stirring to dissolve until the solution is completely clarifiedCleaning to obtain a front liquid B;
s4, adding the silica sol into purified water according to the required amount, and stirring until the silica sol is fully dissolved to obtain a pre-liquid C;
s5, mixing the front liquid A, the front liquid B and the front liquid C, adding the required amount of acid resin while stirring, and uniformly stirring;
s6, adjusting the pH value of the solution to 2.0-4.0 by using a pH adjusting agent in the uniform solution of S5, and finally, complementing the balance with purified water to obtain the environment-friendly coating pretreatment solution.
Preferably, the pH adjuster is a sulfuric acid solution with a mass fraction of 10% or a sodium hydroxide solution with a mass fraction of 10%.
Preferably, the silica sol is acidic SiO with the particle size of 10nm 2 And the acidic resin is aqueous polyurethane.
The use method of the environment-friendly coating pretreatment liquid comprises the following steps: soaking the part to be plated after degreasing, derusting and activating treatment in an environment-friendly pre-coating treatment solution for 10-20 min, drying at the temperature lower than 150 ℃ for 20min, and then performing coating treatment; and during the soaking period, the pH value of the environment-friendly coating pretreatment liquid is kept between 2.0 and 4.0.
The invention also provides a plated part prepared by using the environment-friendly coating pretreatment liquid.
The invention has the beneficial effects that:
the environment-friendly pre-coating treatment liquid provided by the invention mainly takes the fluorine zirconium salt and the acid resin as main film forming systems, and the added silica sol and KH-550 can improve the functions of the fluorine zirconium salt and the acid resin in the aspects of poor water resistance, poor temperature resistance and the like. Meanwhile, the silica sol and KH-550 can also be used for modifying, filling and bonding the silica sol and the acidic resin to form a passivation layer with higher corrosion resistance, and simultaneously, more hydrophilic coating groups are added to improve the binding force of the coating.
The environment-friendly coating pretreatment liquid provided by the invention has the characteristic that an inorganic system and a metal matrix react quickly to form a film quickly, and meanwhile, on one hand, a hydrophilic functional group of the organic system can be combined with reaction bonds such as inorganic salt ions and the metal matrix to form a changeable three-dimensional structure, so that the electrochemical corrosion of the metal matrix is prevented for a long time, and on the other hand, the organic system and a coating layer are mutually staggered, interpenetrated and occluded to form a plurality of organic bonding reaction chains, so that the bonding force between the coating layer and the metal matrix is further improved.
The silica sol is acidic SiO with particle diameter of 10nm 2 Nano SiO modified with KH-550 in a dispersion (pH 2-4) 2 In the system, the lower surface energy of Si enables the Si to migrate and concentrate to the outer surface of the water-based polyurethane film, so that the surface performance of the water-based polyurethane film is enhanced, and the water resistance of the water-based polyurethane film is improved. Meanwhile, the enriched waterborne polyurethane film has the advantages of reduced surface energy, reduced water absorption, remarkably improved tensile strength, improved thermal stability and the like, can further improve the corrosion resistance of the steel before coating, and simultaneously improves the binding force between the steel and the coating layer.
The KH-550 has the following two main effects: (1) Si-O in the silane coupling agent which takes-Si-O-Si-as the framework has excellent thermal stability and low surface energy, so that the Si-O can be used for improving the thermal stability, water resistance and corrosion resistance of the waterborne polyurethane; (2) the silane coupling agent contains groups which can be both hydrophilic and inorganic, and can be used as a bridge for connecting inorganic matters and organic matters to form a bonding layer of an organic layer of the silane coupling agent of the inorganic layer.
Modification of silica sol (i.e., SiO) with KH-550 2 ) Then the modified waterborne polyurethane has certain oleophylic property, and then the modified waterborne polyurethane and acidic resin (namely waterborne polyurethane) generate in-situ polymerization reaction to generate a composite material with excellent comprehensive performance, so that the properties of the modified waterborne polyurethane, such as hardness, thermal stability and the like, are improved.
The nucleophilic addition reaction of KH-550 surface amino and epoxy group of acid resin (i.e. aqueous polyurethane) improves the properties of poor water resistance and temperature resistance of epoxy resin, further reduces the surface energy, water absorption and tensile strength of the aqueous polyurethane film.
The preparation process of the waterborne polyurethane follows a gradual polymerization mechanism, no peculiar smell exists, monomers and other small molecules basically have no residues, the environmental protection property is better than that of the traditional acrylic acid, and meanwhile, a polyurethane resin system has good mechanical property and excellent chemical corrosion resistance.
Finally, Si-O-Si crosslinking points are formed through dehydration condensation between silanol, the water absorption of the polyurethane film can be reduced through forming a three-dimensional network structure, and the surface hydrophobicity of the polyurethane film can be improved due to the fact that the silicon-containing substance has low surface energy.
The system is added into a zirconium fluoride salt vitrification solution to obtain the environment-friendly coating pretreatment solution, and a novel pretreatment film layer before coating can be formed on the surface of a coated part. The film layer has the following characteristics: (1) filling and bonding the vitrified film layer to form a novel protective film layer before metal coating; (2) resin affinity coating layer groups are added in the system, and the binding force of a subsequent coating layer can be improved to a great extent after a film layer is deposited on the surface of a metal workpiece through reaction.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
An environment-friendly coating pretreatment liquid, wherein each liter of the coating pretreatment liquid contains:
H 2 ZrF 6 ：3.0g，Mn(NO 3 ) 2 ：3.0g，Na 2 SO 4 ·10H 2 o: 0.45g, silica sol: 0.35g, KH-550: 1.1g, absolute ethanol: 4.5g, acid resin: 0.75g, pH value regulator and the balance of purified water.
The pH value regulator is a sulfuric acid solution with the mass fraction of 10% or a sodium hydroxide solution with the mass fraction of 10%, and is added according to actual conditions to adjust the pH value of the environment-friendly coating pretreatment liquid to 2.0-4.0.
The silica sol is acidic SiO with particle diameter of 10nm 2 The acidic resin of the dispersion liquid is aqueous polyurethane.
The preparation method of the environment-friendly coating pretreatment liquid comprises the following steps (taking 1L as an example):
s1, weighing raw materials of each component with required mass and required concentration according to the formula;
s2, taking 1/3L pure water, sequentially dissolving KH-550 and absolute ethyl alcohol in the pure water, and stirring to dissolve until the solution is clear to obtain a front liquid A;
s3, taking 1/4L pure water, and mixing H 2 ZrF 6 、Mn(NO 3 ) 2 And Na 2 SO 4 ·10H 2 Dissolving O in purified water in sequence, stirring and dissolving until the solution is completely clarified to obtain a front liquid B;
s4, taking 1/4L pure water, adding the silica sol into the pure water according to the required amount, and stirring until the silica sol is fully dissolved to obtain a front liquid C;
s5, mixing the front liquid A, the front liquid B and the front liquid C, adding the required amount of acid resin while stirring, and uniformly stirring;
s6, adjusting the pH value of the solution to 2.0-4.0 by using a pH adjusting agent in the uniform solution of S5, and finally, complementing the volume of the solution to 1L by using purified water to obtain the environment-friendly pre-coating treatment solution.
Example 2
An environment-friendly coating pretreatment liquid, wherein each liter of the coating pretreatment liquid contains:
H 2 ZrF 6 ：4.0g，Mn(NO 3 ) 2 ：4.0g，Na 2 SO 4 ·10H 2 o: 0.5g, silica sol: 0.4g, KH-550: 1.2g, absolute ethanol: 6g, acidic resin: 1.0g, pH value regulator and the balance of purified water.
The pH value regulator is a sulfuric acid solution with the mass fraction of 10% or a sodium hydroxide solution with the mass fraction of 10%, and is added according to actual conditions to adjust the pH value of the environment-friendly coating pretreatment liquid to 2.0-4.0.
The silica sol is acidic SiO with particle diameter of 10nm 2 The acidic resin of the dispersion liquid is aqueous polyurethane.
The preparation method is the same as that of example 1.
Example 3
An environment-friendly coating pretreatment liquid, wherein each liter of the coating pretreatment liquid contains:
H 2 ZrF 6 ：2.5g，Mn(NO 3 ) 2 ：3.5g，Na 2 SO 4 ·10H 2 o: 0.43g, silica sol: 0.35g, KH-550: 1.15g, anhydrous ethanol: 5.75g, acidic resin: 0.8g, pH value regulator and the balance of purified water.
The pH value regulator is a sulfuric acid solution with the mass fraction of 10% or a sodium hydroxide solution with the mass fraction of 10%, and is added according to actual conditions to adjust the pH value of the environment-friendly coating pretreatment liquid to 2.0-4.0.
The silica sol is acidic SiO with particle diameter of 10nm 2 The acidic resin of the dispersion liquid is aqueous polyurethane.
The preparation method is the same as in example 1.
Comparative example
Comparative example 1: on the basis of example 1, the addition of acidic resin and silica sol was eliminated.
Comparative example 2: on the basis of the embodiment 1, the addition of acidic resin is cancelled, and a silane coupling agent KH-550 is replaced by KH-570, and acidic nano-silica is replaced by nano-magnesium dioxide.
The workpieces are respectively treated by the pre-coating treatment liquids obtained in the examples 1-3 and the comparative examples 1-2, the treatment base material is a No. 10 cold-rolled steel piece, and the specific treatment process of the No. 10 cold-rolled steel piece is as follows:
pre-degreasing → water washing → rust removal → water washing → activation → water washing → pre-plating treatment liquid (time is unified for 10-20 min, pH value is 2.0-4.0, temperature is room temperature) → plating (adopting powder coating) → baking and curing → performance test.
1. Test method
1) Film formation appearance: and (5) inspecting the color and the film thickness of the prepared plastic-sprayed coating.
2) Cross-cut neutral salt spray resistance: refer to GB/T10125 and 2012 salt fog test for artificial atmosphere corrosion test:
directly performing NSS salt spray test on the bare base material after the bare base material is treated by the treatment fluid, and recording the time when rust points appear.
And secondly, conducting NSS salt spray test on the plastic spraying sample piece for 500H.
3) And (3) marking a hundred grids for testing: reference is made to the scratch test for paint films of GB/T9286-1998 color paints and varnishes: and (5) carrying out a hundred-grid test on the spray molding sample piece.
4) T bend test: refer to GB/T30791-: and (5) carrying out T-bend test on the plastic spraying sample piece.
5) And (3) testing the cupping: refer to GB/T9753 2007 color paint and varnish cupping test: and (5) carrying out a cupping test on the plastic spraying sample piece.
2. Results and analysis
The results of testing the film forming properties of examples 1-3 and comparative examples 1-2 are shown in Table 1 below.
TABLE 1 test results
It can be seen that after the steel workpiece is treated by the environment-friendly coating pretreatment liquid prepared in the embodiments 1-3, the average salt spray resistance test of the bare steel NSS is about 58min, which is much higher than the average 14min of the comparative example; after spraying, the NSS salt spray resistance test is 500H, the average corrosion width is 0.90mm and is smaller than the values of 2.60 mm and 2.78mm of the comparative example, and the marking test, the T bend test and the cupping test are all qualified. The film formed by the environment-friendly coating pretreatment liquid has the comprehensive performance of long inter-process corrosion resistance time and obviously improved coating and plating binding force.
The above is only a preferred embodiment of the present invention, and is not intended to limit the invention; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that: any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. An environment-friendly coating pretreatment liquid is characterized in that each liter of the coating pretreatment liquid contains:
H 2 ZrF 6 ：2.0～4.0g，
Mn(NO 3 ) 2 ：2.0～4.0g，
Na 2 SO 4 ·10H 2 O：0.4～0.5g，
acid resin: 0.5 to 1.0g of a surfactant,
silica sol: 0.3 to 0.4g of a mineral,
KH-550：1.0～1.2g，
anhydrous ethanol: 3.0 to 6.0g of a mineral oil,
a pH value regulator, and a pH value regulator,
the balance of purified water;
the pH value of the environment-friendly coating pretreatment liquid is 2.0-4.0.
2. The environment-friendly pre-coating treatment solution according to claim 1, wherein the pH regulator is a sulfuric acid solution with a mass fraction of 10% or a sodium hydroxide solution with a mass fraction of 10%.
3. The environment-friendly pre-coating treatment solution as defined in claim 2, wherein each liter of the pre-coating treatment solution contains H 2 ZrF 6 4.0g，Mn(NO 3 ) 2 4.0g，Na 2 SO 4 ·10H 2 0.5g of O, 1.0g of acid resin, 0.4g of silica sol, KH-5501.2 g, 6.0g of absolute ethyl alcohol, a pH value regulator and the balance of purified water.
4. The environment-friendly pre-coating treatment solution as defined in claim 1, wherein the silica sol has a particle size of 10nm and is SiO 2 Acidic SiO with mass content more than or equal to 30 percent 2 And (3) dispersing the mixture.
5. The environment-friendly pre-coating treatment solution according to claim 1, wherein the acidic resin is aqueous polyurethane.
6. The preparation method of the environment-friendly pre-coating treatment liquid as claimed in claim 1 or 3, characterized by comprising the following steps:
s1, weighing raw materials of each component with required mass and required concentration;
s2, sequentially dissolving KH-550 and ethanol in a certain amount of purified water, and stirring to dissolve until the solution is clear to obtain a front liquid A;
s3, mixing H 2 ZrF 6 、Mn(NO 3 ) 2 And Na 2 SO 4 ·10H 2 Dissolving O in a certain amount of purified water in sequence, stirring and dissolving until the solution is completely clarified to obtain a front liquid B;
s4, adding silica sol into purified water according to the required amount, and stirring until the silica sol is fully dissolved to obtain a front liquid C;
s5, mixing the front liquid A, the front liquid B and the front liquid C, adding the required amount of acid resin while stirring, and uniformly stirring;
s6, adjusting the pH value of the solution to 2.0-4.0 by using a pH adjusting agent in the uniform solution of S5, and finally, complementing the balance with purified water to obtain the environment-friendly pre-coating treatment solution.
7. The method according to claim 6, wherein the pH adjuster is a 10% by mass sulfuric acid solution or a 10% by mass sodium hydroxide solution.
8. The method according to claim 6, wherein the silica sol is acidic SiO having a particle size of 10nm 2 And the acidic resin is aqueous polyurethane.
9. The use method of the environment-friendly pre-coating treatment solution as defined in any one of claims 1 to 5, wherein the part to be coated, which is subjected to degreasing, rust removal and activation treatment, is immersed in the environment-friendly pre-coating treatment solution for 10 to 20min, then dried at a temperature lower than 150 ℃ for 20min, and then is subjected to coating treatment; and maintaining the pH value of the environment-friendly coating pretreatment liquid at 2.0-4.0 during the soaking period.
10. A plated article prepared by using the environment-friendly pre-plating treatment liquid as defined in any one of claims 1 to 5.
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