CN105255338B - Galvanized steel plain sheet with excellent surface wear resistance, corrosion resistance and resistance to acid and alkali and aqueous surface-treating agent - Google Patents
Galvanized steel plain sheet with excellent surface wear resistance, corrosion resistance and resistance to acid and alkali and aqueous surface-treating agent Download PDFInfo
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- CN105255338B CN105255338B CN201510705304.2A CN201510705304A CN105255338B CN 105255338 B CN105255338 B CN 105255338B CN 201510705304 A CN201510705304 A CN 201510705304A CN 105255338 B CN105255338 B CN 105255338B
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- 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
- C23C22/68—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 solutions with pH between 6 and 8
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- 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
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- 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
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- 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
- C23C22/74—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 for obtaining burned-in conversion coatings
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
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Abstract
With excellent surface wear resistance, the galvanized steel plain sheet and aqueous surface-treating agent of corrosion resistance and resistance to acid and alkali, by containing waterborne cation polyurethane compound resin in galvanized steel sheet surface coating solidification, include the complex type organic silicon alkane coupling agent of double organic alkane coupling agent and single organo silane coupling agent, include the composite lubricated particle of ptfe surface modification high-density polyethylene particle, graphene oxide, water-soluble fluorine-containing compound, the surface conditioning agent of the compositions such as water-soluble phosphorus-containing compound and water-solubility rare-earth salt compounds, obtain the surface abrasion resistance for having excellent, the surface treatment galvanized steel plain sheet of corrosion resistance and resistance to acid and alkali, the surface treatment galvanized steel plain sheet also has the good resistance such as solvent resistance etc. to all kinds of chemical mediators simultaneously.
Description
Technical field
The invention belongs to technical field of metal material surface treatment, and in particular to one kind have excellent surface wear resistance,
The galvanized steel plain sheet and aqueous surface-treating agent of corrosion resistance and resistance to acid and alkali.
Background technology
Galvanized steel plain sheet is widely used in the every field such as automobile, household electrical appliances and building, is used as automobile, household electrical appliance, OA more
The parts such as product use.But during galvanized steel plain sheet stores in a warehouse transport and processing use, there are multiple critical issues to need to pay close attention to,
For example, generating white rust to prevent galvanized steel plain sheet from corrosion occurs during transporting and storing, antirust oil is applied when producing steel plate；For
Reduce friction during punch forming between mold and plank, prevent plank cracking and the scratch of surface zinc layers, part punching at
To add lubricating oil when type to mold, carry out cleaning by degreasing after molding again, degreasing agent can be divided into solvent type degreasing agent and alkaline degreasing
Agent.
In the entire storage and transportation of galvanized steel plain sheet, punching course, the use of antirust oil, lubricating oil and degreasing agent is to environment and life
It is all unfavorable to produce cost.In order to improve corrosion resistance and processing forming, past method mainly carries out chromium to galvanized steel plain sheet
Sour passivated surface processing, this method can improve steel plate corrosion resistance, but improve to its processing forming and other resistances limited；
Or on the basis of chromating be coated with auxiliary agent containing solid lubrication (be usually low surface energy polymeric, as polyolefin with
Polytetrafluoroethylene (PTFE)) organic resin meet the anti-corrosion and molding requirement of steel plate to take into account anti-corrosion and lubricant effect, it is still, this
The surface treated steel plate produced using such method contains chromium, in use chromium be precipitated can to human body and
Environment causes damages.
Galvanized steel plain sheet is surface-treated when OA products or vending machine industry are as internal naked appliance, it can be with paper, beverage bottle
Or food casing bag contacts friction repeatedly, to prevent surface of steel plate to be worn during with external substance multiple-contact,
There is the problem of follow-up corrosion resistance of steel plate is remarkably decreased.Meanwhile be surface-treated galvanized steel plain sheet as external shell in Electric Appliance Cabinet and
The industries such as cabinet cause surface blackening to influence appearance in use, the also often generation phase mutual friction in shell transportational process.The above feelings
Condition requires that galvanized steel sheet surface has good wear resistance.
To improve galvanized steel sheet surface wear resistance, the production technology of two-step method is typically used, is carried out in surface of steel plate
Chromating plays the role of enhancing coating adhesion.Then it is coated with the polymer epithelium of thicker (being more than 5 microns), is risen
To the effect of strengthening surface wear resistance.But the softening temperature of usual polymer epithelium is relatively low, mold during continuous punching
It is damaged that fever is easy to cause epithelium softening.Meanwhile with the appearance of environmental protection instruction, containing chromium-treated galvanized steel plain sheet also gradually by ring
Guarantor's type product is replaced.
Secondly, notch antirust is issues that need special attention during galvanized steel plain sheet use.Phosphorating treatment is very after degreasing
A kind of common notch antirust care method that conglomerate uses at present, it is specific as follows：It is advanced to punching parts after punch process
Then the alkalinity degreasing of row short time carries out phosphorating treatment again, so that part incision site is generated one layer of phosphating coat, the phosphating coat is to cutting
Mouth plays a protective role, still, the alkali (alkaline defatting agent solution, the general 9-11 of pH value) in the processing procedure and sour (phosphatization
Liquid, the general 3-4 of pH value) can all destruction be played to the surface epithelium for being surface-treated galvanized steel plain sheet, to influence the resistance to of epithelium
Abrasiveness and follow-up corrosion resisting property, therefore such application field is high to the resistance to acid and alkali requirement for being surface-treated galvanized steel plain sheet.
Chinese patent CN104449154A provides a kind of aqueous chromium-free fingerprint-resistant coating for galvanized steel plain sheet, by this
Coating treated steel plate has excellent corrosion resistance and alkali resistance degreasing.But it is not referred in the patent after coating processing
Galvanized steel plain sheet surface abrasion resistance, processing forming and acid resistance.However, in OA products or vending machine industry, steel plate
Surface can contact friction repeatedly with paper, beverage bottle or food casing bag, and the surface epithelium of the surface treated steel plate may hold
It is easily worn with the multiple friction process of external substance, the problem of steel plate corrosion resistance is remarkably decreased occurs.
Chinese patent CN102272253A provide a kind of surface of steel plate processing resin combination containing graphene and
Utilize the surface treated steel plate of the composition.The resin combination is made of binder resin, graphene and solvent, utilizes this
The processed steel plate of resin combination has good electric conductivity, corrosion resistance, adhesion and processability.
Graphene is a kind of new material for the two-dimension single layer laminated structure for having carbon atom to constitute, and can be layering and be covered in
Matrix surface forms dense coating, plays the role of excellent physical isolation.Evenly dispersed graphene sheet layer in the coating can increase
The permeation pathway that big corrosive medium infiltrates into base material effectively carries so as to prevent destruction of the corrosive medium to base material for a long time
The corrosion resistance of high coating.Meanwhile between each atom of graphene being that carbon-to-carbon is covalently keyed, lamella is model moral with piece interlayer
Hua Li, therefore piece interlayer is easy mutually sliding, has excellent mechanical performance and self-lubricating property, therefore graphene can rise again
Effect to enhancing wear resistance still since graphene sheet layer and piece interlayer Van der Waals force are stronger, was being used in graphene
Monolithic graphite alkene piece interlayer is easy to happen lamella reunion in journey, and is formed compared with macro aggregate, and in aqueous body in water-based system
Precipitation is quickly precipitated in system, to not have the purpose of increase system mechanical strength and wear resistance.
Invention content
The purpose of the present invention is to provide it is a kind of with excellent surface wear resistance, corrosion resistance and resistance to acid and alkali galvanized steel
Plate meets multiple fields user to the environmental protection of galvanized steel plain sheet, the requirement of surface abrasion resistance damage, punch process and defatting-bonderizing, is somebody's turn to do
Galvanized steel plain sheet is surface-treated also with the good resistance such as solvent resistance etc. to all kinds of chemical mediators.
Specifically, surface abrasion resistance includes steel ball under appearance and high/low temperature after surface of steel plate lubricity, punch process
The repeatedly appearance after friction；Corrosion resistance includes the corrosion resistance after corrosion resistance and defatting-bonderizing after tablet corrosion resistance, molding；Acid and alkali-resistance
Property includes acid resistance, alkali resistance and resistance to defatting-bonderizing.
By arduous research, find by containing the compound tree of waterborne cation polyurethane in galvanized steel sheet surface coating solidification
Fat, includes polytetrafluoroethyl-ne at the complex type organic silicon alkane coupling agent comprising double organic alkane coupling agent and single organo silane coupling agent
Alkene-composite lubricated the particle of surface modification high-density polyethylene particle, graphene oxide, water-soluble fluorine-containing compound, water solubility
The surface treatment galvanized steel plain sheet that the surface conditioning agents of the compositions such as phosphorus-containing compound and water-solubility rare-earth salt compounds is formed, can be with
Reach above-mentioned purpose, thereby completing the present invention.
Meanwhile it can stablize at the environment-friendly type aqueous surface for manufacturing above-mentioned surface treatment galvanized steel plain sheet the present invention also provides a kind of
Manage agent.
Technical scheme is as follows：
It is a kind of with excellent surface wear resistance, corrosion resistance and resistance to acid and alkali galvanized steel plain sheet, surface be covered with it is organic-
Inorganic compounding epithelium, the epithelium contain：
A) waterborne cation polyurethane compound resin, the parts by weight in epithelium are 30-50 parts；
The waterborne cation polyurethane compound resin is by polytetrahydrofuran ether, polyacrylate or poly- perfluoroalkyl
One or more and base polyurethane prepolymer for use as in acid esters is copolymerized, relative molecular weight 80000-150000；
B) complex type organic silicon alkane coupling agent, the parts by weight in epithelium are 20-45 parts；
The complex type organic silicon alkane coupling is at least one double organic alkane coupling agent and at least one single organosilan
The mixture of coupling agent；The double organic alkane coupling agent contains bridging structure, the double organic alkane coupling agent and single organosilicon
The weight ratio of alkane coupling agent is 0.3-2；
C) composite lubricated particle, the parts by weight in epithelium are 15-25 parts；The composite lubricated particle includes polytetrafluoroethyl-ne
Alkene particle and surface modification high-density polyethylene particle；
D the parts by weight of) graphene oxide water solution, wherein graphene oxide in epithelium are 0.1-0.5 parts；The oxygen
In graphite aqueous solution, the mass fraction of graphene oxide is 1-5%；
E the parts by weight of) water-soluble fluorine-containing compound, wherein fluorine element in epithelium are 0.5-1.5 parts；
F) water-soluble phosphorus-containing compound, wherein parts by weight of the P elements in epithelium are 1-2 parts；
G) water-solubility rare-earth salt compounds, parts by weight of the rare earth elements in epithelium are 0.1-1.5 parts.
In the above-mentioned galvanized steel plain sheet with excellent surface wear resistance, corrosion resistance and resistance to acid and alkali：
The Organic-inorganic composite protective film is single layer structure, and film thickness range is 2-4 microns.
Further, the waterborne cation polyurethane compound resin (A) is by being selected from polytetrahydrofuran ether, polyacrylic acid
At least one of ester or poly- perfluoroalkyl acrylate are copolymerized with base polyurethane prepolymer for use as, wherein the polyurethane is pre-
Aggressiveness be by polytetrahydrofuran diol, Polyoxyethylene glycol or polycaprolactone glycol etc. without containing ester group polyol compounds with
Aliphatic isocyanates or aromatic isocyanate compound reaction obtain, the waterborne cation polyurethane compound resin
For relative molecular weight in 80000-150000, the parts by weight in epithelium are 30-50 parts, preferably 35-45 parts.
In the complex type organic silicon alkane coupling agent (B), the bridging structure of the double organic alkane coupling agent is by 2-4
Methylene, amino or sulfydryl form, and at least contain in the molecule of single organo silane coupling agent reactive there are one having
Group, described to have reactive group for amino, epoxy group or vinyl, the complex type organic silicon alkane coupling agent (B)
Weight ratio with waterborne cation polyurethane compound resin (A) is 0.5-1.5.
The weight ratio of polytetrafluoroethylparticle particle and surface modification high-density polyethylene particle in the composite lubricated particle (C)
For 1-3, the polytetrafluoroethylparticle particle diameter (middle several diameters) is 0.3-0.8 microns, and the surface modification high-density is poly-
Beta particles diameter (middle several diameters) is 3-5 microns, and the surface modification high-density polyethylene particle surface is grafted with reaction
Property group, the reactive group be amino, hydroxyl, carboxyl, epoxy group or carbamate groups in it is one or more.
In the graphene oxide water solution (D), the graphene oxide is single layer or multilayer, works as graphene oxide
For multilayer when, piece layer number be 5 layers or less.
Further, the graphene oxide water solution (D) is surface-functionalized graphene oxide water solution, the surface
Functional graphene oxide refers to being grafted with hydrophily reactive group in surface of graphene oxide, and the hydrophily reactive group is
It is one or more in amino, hydroxyl and carboxyl.
The water-soluble fluorine-containing compound (E) is fluorine-containing metallic salt or fluorine-containing acids, for example, water-soluble fluorine-containing
Compound can be one or more in sodium fluoride, ammonium titanium fluoride, prodan, hexafluorotitanic acid and fluosilicic acid.
The water-soluble phosphorus-containing compound (F) is phosphoric acid salt or phosphorous acids, for example, water-soluble phosphorous chemical combination
Object can be one in orthophosphoric acid, pyrophosphoric acid, tripolyphosphate, three poly-metaphosphoric acids, ammonium phosphate, aluminium triphosphate and ammonium polyphosphate
Kind is a variety of.
The water-solubility rare-earth salt compounds (G) are at least one in rare earth cerium salt, La-salt and rare earth zirconates
Kind, for example, rare earth cerium salt can be cerous nitrate, cerous sulfate, can also be in fluorine-containing cerium salt or cerium ammonium compound salt
It is one or more；La-salt can be one or more in lanthanum chloride, lanthanum sulfate and lanthanum nitrate；Rare earth zirconates can be zirconium
It is one or more in potassium fluorozirconate, zirconium nitrate and zirconium sulfate.
A kind of surface treating agent for galvanized steel sheet with excellent surface wear resistance, corrosion resistance and resistance to acid and alkali, water
Total solid part contains following component in solution：
A) waterborne cation polyurethane compound resin, the parts by weight in epithelium are 30-50 parts；The waterborne cation is poly-
The relative molecular weight of urethane compound resin is 80000-150000, by polytetrahydrofuran ether, polyacrylate or poly- perfluoroalkyl
One or more and base polyurethane prepolymer for use as in acrylate is copolymerized；
B) complex type organic silicon alkane coupling agent, the parts by weight in epithelium are 20-45 parts；
The complex type organic silicon alkane coupling is at least one double organic alkane coupling agent and at least one single organosilan
The mixture of coupling agent；The double organic alkane coupling agent contains bridging structure, the double organic alkane coupling agent and single organosilicon
The weight ratio of alkane coupling agent is 0.3-2；
C) composite lubricated particle, the parts by weight in epithelium are 15-25 parts；The composite lubricated particle includes polytetrafluoroethyl-ne
Alkene particle and surface modification high-density polyethylene particle；
D the parts by weight of) graphene oxide water solution, wherein graphene oxide in epithelium are 0.1-0.5 parts；The oxygen
In graphite aqueous solution, the mass fraction of graphene oxide is 1-5%；
E the parts by weight of) water-soluble fluorine-containing compound, wherein fluorine element in epithelium are 0.5-1.5 parts；
F) water-soluble phosphorus-containing compound, wherein parts by weight of the P elements in epithelium are 1-2 parts；
G) water-solubility rare-earth salt compounds, parts by weight of the rare earth elements in epithelium are 0.1-1.5 parts.
Further, the waterborne cation polyurethane compound resin (A) is by being selected from polytetrahydrofuran ether, polyacrylic acid
At least one of ester or poly- perfluoroalkyl acrylate are copolymerized with base polyurethane prepolymer for use as, wherein the polyurethane is pre-
Aggressiveness be by polytetrahydrofuran diol, Polyoxyethylene glycol or polycaprolactone glycol etc. without containing ester group polyol compounds with
Aliphatic isocyanates or aromatic isocyanate compound reaction obtain, the relative molecular weight of the polyurethane compound resin
In 80000-150000, the parts by weight in epithelium are 30-50 parts, preferably 35-45 parts.
In the complex type organic silicon alkane coupling agent (B), the bridging structure of the double organic alkane coupling agent is by 2-4
Methylene, amino or sulfydryl form, and at least contain in the molecule of single organo silane coupling agent reactive there are one having
Group, described to have reactive group for amino, epoxy group or vinyl, the complex type organic silicon alkane coupling agent (B)
Weight ratio with waterborne cation polyurethane compound resin (A) is 0.5-1.5.
The weight ratio of polytetrafluoroethylparticle particle and surface modification high-density polyethylene particle in the composite lubricated particle (C)
For 1-3；The polytetrafluoroethylparticle particle diameter (middle several diameters) is 0.3-0.8 microns, and the surface modification high-density is poly-
Beta particles diameter (middle several diameters) is 3-5 microns, and the surface modification high-density polyethylene particle surface is grafted with reaction
Property group, the reactive group be amino, hydroxyl, carboxyl, epoxy group or carbamate groups in it is one or more.
In the graphene oxide water solution (D), the graphene oxide is single layer or multilayer, works as graphene oxide
For multilayer when, piece layer number be 5 layers or less.
Further, the graphene oxide water solution (D) is surface-functionalized graphene oxide water solution, the surface
Functional graphene oxide refers to being grafted with hydrophily reactive group in surface of graphene oxide, and the hydrophily reactive group is
It is one or more in amino, hydroxyl and carboxyl.
The water-soluble fluorine-containing compound (E) is fluorine-containing metallic salt or fluorine-containing acids, for example, water-soluble fluorine-containing
Compound can be one or more in sodium fluoride, ammonium titanium fluoride, prodan, hexafluorotitanic acid and fluosilicic acid.
The water-soluble phosphorus-containing compound (F) is phosphoric acid salt or phosphorous acids, for example, water-soluble phosphorous chemical combination
Object can be one in orthophosphoric acid, pyrophosphoric acid, tripolyphosphate, three poly-metaphosphoric acids, ammonium phosphate, aluminium triphosphate and ammonium polyphosphate
Kind is a variety of.
The water-solubility rare-earth salt compounds (G) are at least one in rare earth cerium salt, La-salt and rare earth zirconates
Kind, for example, rare earth cerium salt can be cerous nitrate, cerous sulfate, can also be in fluorine-containing cerium salt or cerium ammonium compound salt
It is one or more；La-salt can be one or more in lanthanum chloride, lanthanum sulfate and lanthanum nitrate；Rare earth zirconates can be zirconium
It is one or more in potassium fluorozirconate, zirconium nitrate and zirconium sulfate.
It is also an object of the present invention to provide a kind of with excellent surface wear resistance, corrosion resistance and resistance to acid and alkali
The preparation method of galvanized steel plain sheet forms aqueous table by the component of the aqueous surface-treating agent by being dissolved or dispersed in water
The aqueous surface-treating agent is coated to surface by a roller coating, and is dried between 80-180 DEG C by surface treatment agent,
Make thickness of dry film at 2-4 microns.
The waterborne cation polyurethane compound resin that the present invention uses, containing cationic hydrophilic groups, in aqueous medium
Water solubility is can behave as, or therefore it can be aqueous solution to form water-base resin by Forced Dispersion, can also be moisture
Dissipate type.
The present invention reduces to the greatest extent can be with the group of acid-base reaction, such as ester group in waterborne cation polyurethane compound resin
Deng so that the epithelium formed has excellent resistance to acid and alkali.Waterborne cation polyurethane compound resin used in the present invention is
By the one or more and base polyurethane prepolymer for use as copolymerization in polytetrahydrofuran ether, polyacrylate or poly- perfluoroalkyl acrylate
Form, wherein polytetrahydrofuran ether, polyacrylate or poly- perfluoroalkyl acrylate have good chemical resistance and
Physical mechanical property can not only enhance the acid-proof alkaline and solvent resistance of epithelium, additionally it is possible to epithelial surfaces hardness is improved,
To enhance the abrasion resistance properties of epithelium.In the waterborne cation polyurethane compound resin of the present invention, base polyurethane prepolymer for use as can
To be the polyol compounds and fat for not containing ester group by polytetrahydrofuran diol, Polyoxyethylene glycol or polycaprolactone glycol etc.
Fat race isocyanates or aromatic isocyanate compound reaction obtain, without using makrolon polyalcohols and polyester containing ester group
Polyalcohols synthesis of polyurethane performed polymer.
Waterborne cation polyurethane compound resin used in the present invention, model of the relative molecular weight in 80000-150000
In enclosing, if its relative molecular weight discontented 80000, the hardness of epithelium entirety is inadequate, so as to lead to the wear resistance of epithelium
It is insufficient；If its relative molecular weight is more than 150000, epithelium flexibility declines, elongation percentage reduces, and in punch process, epithelium is not
With substrate deformation, it is bad to may result in material processability.
Waterborne cation polyurethane compound resin used in the present invention, shared parts by weight are 30-50 parts in epithelium, such as
Fruit is less than 30 parts, and wear resistance, punching formation property, solvent resistance and the corrosion resistance of epithelium can reduce；If it exceeds 50 parts, epithelium
Resistance to acid and alkali may reduce, preferred weight part be 35-45 parts.
In the complex type organic silicon alkane coupling agent of the present invention, double organic alkane coupling agent refers to having in same molecular structure
Two silane structures have 6 alkoxy grps on one molecule, are twice of common single organo silane coupling agent, of the invention is double
Organo silane coupling agent contains bridging structure, and bridging structure can be made of 2-4 methylene, amino or sulfydryl, other structures
Make that there is no particular limitation, for example, 1,2- bis- trimethoxy silicon substrate ethane, the bis- second methoxyl group silicon substrate ethane of 1,2-, it is double-
(γ-triethoxy silicon substrate propyl) tetrasulfide, double-[γ-(triethoxysilicane) propyl]-disulphide, double-(γ-trimethoxy
Base silicon substrate propyl) the similar constituent such as amine can use, and use unlike conventional single organo silane coupling agent, and it is of the invention
Used in double organic alkane coupling agent in there are 6 alkoxy grps for reaction, the coupling of double organic alkane can be enhanced
Chemical bonding between agent and metal substrate and other components can not only improve the crosslink density of epithelium, reach reinforcing epithelium
Wear resistance and corrosion proof purpose, but also the adhesive force of epithelium and metal substrate can be enhanced.
In the complex type organic silicon alkane coupling agent of the present invention, in each molecule of used list organo silane coupling agent extremely
Few to have reactive group, such as amino, epoxy group or vinyl containing there are one, there is no particular limitation for other constructions, lifts
For example, 3- aminopropyl triethoxysilanes, N- (2- aminoethyls) 3- aminopropyl trimethoxysilanes, 3- epoxy group trimethoxies
Silane, 2- (3,4- 7-oxa-bicyclo[4.1.0 base) ethyl trimethoxy silane, vinyl silane triisopropoxide, vinyl triethoxyl
The similar constituent such as silane can use.
In the complex type organic silicon alkane coupling agent of the present invention, double organic alkane coupling agent and single organo silane coupling agent mix
Afterwards, the two will carry out the prepolymerization of part, the organic silane compound of synthesis can reinforce epithelium Z-direction crosslinking journey
Degree, to make epithelium wear resistance improve, corrosion resistance enhancing.Remaining active group in simultaneously synthesizing organic silane compound
It can be reacted with metal substrate surface, the interface adhesion of enhancing and metal substrate.In epithelium, double organic alkane coupling agent and
The weight ratio of single organo silane coupling agent is preferably in the range of 0.3-2, if it is less than 0.3, that is, the coupling of double organic alkane
When agent is less, the corrosion resistance and adhesive force of epithelium are poor, and being susceptible to epithelium during punch forming falls off, in military service process
In be susceptible to corrosion；If it is greater than 2, that is, when double organic alkane coupling agent is more, double organic alkane coupling agent not Yishui River
Solution be easy to cause inorganic agent layering or reduces inorganic agent storability, used to influence inorganic agent.
The complex type organic silicon alkane coupling agent of the present invention shared parts by weight in epithelium are 20-45 parts, if being less than 20 parts,
The adhesion and corrosion resistance of epithelium can reduce；If it exceeds 45 parts, epithelium ductility is deteriorated, and cracking is easy in forming process,
Lead to the reduction of epithelium punching formation property.
In addition, the complex type organic silicon alkane coupling agent of the present invention and the weight ratio of waterborne cation polyurethane compound resin exist
Between 0.5-1.5, if it is less than 0.5, that is, polyurethane compound resin is more, due to polyurethane compound resin and metal substrate
Chemical bonding ability it is weaker, may cause epithelium adhesion and corrosion resistance decline.If being higher than 1.5, that is, organosilicon
Alkane coupling agent is more, and since the brittleness of organo silane coupling agent is big, elongation percentage is weaker, and epithelium ductility may be caused to be deteriorated,
Cracking is easy in forming process, to influence the follow-up corrosion resisting property of forming part.
Polytetrafluoroethylparticle particle used in the present invention is commercial solid lubricating auxiliary agent, such lubricating auxiliary agent has low table
The characteristics of face energy, high-lubricity and high surface hardness, epithelial surfaces can be moved to rapidly during inorganic agent baking-curing,
To form the lubricant layer of one layer of hard in epithelial surfaces, the wear resistance of epithelium can be not only improved, additionally it is possible to enhance epithelium
Surface slip achievees the purpose that strengthen epithelium punching formation property.Used polytetrafluoroethylparticle particle diameter (middle several diameters)
In 0.3-0.8 microns of range, if being less than 0.3 micron, polytetrafluoroethylparticle particle is too small, is promoted to the wearability of epithelium unknown
It is aobvious；If being higher than 0.8 micron, polytetrafluoroethylparticle particle is excessive, and sole mass is heavier, is not easy in epithelium solidification process to epithelium
Surface migration, therefore cannot complete hard lubricant layer be formed in epithelial surfaces again, not having improves epithelial surfaces slipping
Purpose.
Modification high-density polyethylene particle in surface used in the present invention is commercial solid lubricating auxiliary agent, such lubrication helps
Agent particle surface is grafted with reactive group, and reactive group is in amino, hydroxyl, carboxyl, epoxy group or carbamate groups
It is one or more.Wherein, high density polyethylene (HDPE) is manufactured usually using Ziegler-Natta polymerizations, without branch on strand
Chain, strand arrangement is regular, has higher density, common density is in 0.940~0.976g/cm3In range, hydroxyl and
Carboxyl can be obtained by the way that high density polyethylene (HDPE) particle to be immersed in strong oxidizing solution；Amino and carbamate groups can be with
It is obtained by ethylenediamine, hexamethylene diamine or urethanes and the grafting of high density polyethylene (HDPE) particle surface；Epoxy group can pass through
Glycidyl methacrylate or allyl glycidyl ether are obtained with the grafting of high density polyethylene (HDPE) particle surface.The above reaction
Property group can react to each other to form covalent key connection with organo silane coupling agent in treatment fluid, it is poly- can not only to reinforce high density
Beta particles and epithelium adhesion strength, additionally it is possible to high density polyethylene (HDPE) particle is held onto, to ensure high density polyethylene (HDPE) particle
It can be dispersed in epithelium, excellent wear resistance can be provided in the whole thickness direction of epithelium, improve epithelium punching
Press processability and wear resistance.Meanwhile delaying to corrode by forming the chemical bonding between high density polyethylene (HDPE) particle and epithelium
For medium along high density polyethylene (HDPE) particle surface to epithelium internal penetration, the addition for reducing high density polyethylene (HDPE) particle is anti-corrosion to epithelium
The negative effect of property.
Surface modification high-density polyethylene particle diameter (middle several diameters) used in the present invention in 3-5 microns of ranges,
If being less than 3 microns, high density polyethylene (HDPE) particle does not have the effect of enhancing epithelium wear resistance in epithelium, if being higher than 5
Micron, solid lubrication aid particle is excessive, and most of particle is exposed to epithelial surfaces, and when being rubbed by punching press, big particle holds
Extraction easy to fall off causes the impatient acute decline of the punch process of epithelium.
Composite lubricated ion used in the present invention, polytetrafluoroethylparticle particle and surface modification high-density polyethylene particle
Weight ratio is in the range of 1-3.If being less than 1, that is to say, that the surface modification high-density polyethylene particle being relatively large in diameter is more,
Corrosive medium, to epithelium internal penetration, may lead to the corrosion resistance and table of epithelium readily along major diameter high density polyethylene (HDPE) particle
Face lubricity declines；If being higher than 3, that is, when polytetrafluoroethylparticle particle is more, excessive polytetrafluoroethylparticle particle is enriched in
Epithelial surfaces can cause the abrasion resistance of epithelium inadequate.
Composite lubricated total ion concentration used in the present invention shared parts by weight in epithelium are 15-25 parts.If it is less than 15
Part, then epithelial surfaces lubricity and abrasion resistance are inadequate, and if it is greater than 25 parts, excessive solid lubrication aid particle is present in skin
In film, corrosive medium may be inside solid lubrication auxiliary agent contacting permeation to epithelium, to reduce epithelium corrosion resistance and acidproof
Alkalinity.
In graphene oxide water solution used in the present invention, the mass fraction of graphene oxide is 1-5%, used
Graphene oxide is lamellar structure, can be single layer or multilayer.When graphene oxide is multilayer, piece layer number is preferably 5
Layer or less.By graphene oxide layer number being controlled at 5 layers hereinafter, graphene can be made to keep excellent flexibility, holding epithelium
Flexibility, and improve the wear resistance of epithelium.
Hydrophily reactive group is contained on the surface of surface-functionalized graphene oxide water solution, and mesh can be used in manufacturing method
Preceding well known method, for example, hydroxyl and carboxyl can be molten by the way that graphene oxide to be immersed in 70-80 DEG C of strong oxidizing property
Ultrasonic disperse is handled 1 hour in liquid (such as concentrated sulfuric acid/potassium permanganate mixed solution, the concentrated sulfuric acid/concentrated nitric acid mixed solution), then mistake
It filters and is cleaned to the close neutrality of graphene aqueous solution with a large amount of deionized waters；Amino can pass through ethylenediamine or hexamethylene diamine and oxidation
Graphene surface grafting obtains.
The surface-functionalized surface of graphene oxide of the present invention is grafted hydrophily reactive group, can not only improve oxidation stone
Stably dispersing coefficient of the black alkene in aqueous surface-treating agent system prevents it from reuniting or precipitating；Graphite oxide can also be enhanced
The chemical reaction of alkene and organo silane coupling agent or polyurethane compound resin in system, to improve graphene oxide and other groups
The boundary strength of part, oxidation graphene act on the raising of epithelium corrosion resistance and wear resistance.The oxidation stone of lamellar structure
Black alkene is dispersed in inside epithelium, and when Korrosionsmedium is to epithelium internal penetration, graphene oxide layer can increase corruption
The permeation pathway of corrosion medium plays the role of excellent physical protection, to increase substantially the corrosion resistance of epithelium.Together
When, it is that carbon-to-carbon is covalently keyed between graphene oxide layer atom, there is excellent mechanical performance, to the mill of external object
Damage and destruction have good resistant function, so as to play the role of improving epithelium abrasion resistance properties.
In the graphene oxide water solution or surface-functionalized graphene oxide water solution of the present invention, graphene oxide is in skin
Shared parts by weight are 0.1-0.5 parts in film.If being less than 0.1 part, that is, when graphene oxide is less, graphene oxide is to skin
Film wear resistance and corrosion proof raising unobvious；If being higher than 0.5 part, that is, when graphene oxide is more, epithelium is by oxygen
The influence of graphite alkene is dimmed, influences appearance.Also it is easy to happen reunion when simultaneous oxidation graphene is more, reduces epithelial surfaces matter
Amount.
The water-soluble fluorine-containing compound of the present invention, fluorine element in the fluorochemical shared parts by weight in epithelium are 0.5-
1.5 part.If the parts by weight of fluorine element are less than 0.5 part, that is to say, that when fluorochemical is less, epithelium corrosion resistance may
Decline；If the parts by weight of fluorine element are more than 1.5 parts, that is to say, that when fluorochemical is more, the stabilization of aqueous treatment agent
Property possible deviation.
The water-soluble phosphorus-containing compound of the present invention, P elements in the phosphorus-containing compound shared parts by weight in epithelium are 1-2
Part.If the parts by weight of P elements are less than 1 part, that is to say, that when phosphorus-containing compound is less, without additive effect, epithelium is anti-corrosion
Property may decline；If the parts by weight of P elements are more than 2 parts, that is to say, that when phosphorus-containing compound is more, skin may be caused
Film adhesion is deteriorated.
The present invention water-solubility rare-earth salt compounds, rare earth salts compound can with galvanized steel sheet surface zinc coat and
Hydroxyl reaction in treatment fluid after organo silane coupling agent hydrolysis, forms the metallic bond with high bond energy, in Several Thiourea Derivatives on Zinc Plate Surface shape
At the rare-earth salts conversion film of one layer of thin compact structure, being in direct contact for steel plate and corrosive medium is physically shielded, is reduced
The possibility that steel plate is corroded, to significantly improving the ability for expanding erosion under the anti-film of steel plate.In water-solubility rare-earth salt compounds
Rare earth element in epithelium shared parts by weight be 0.1-1.5 parts.If the parts by weight of rare earth element are less than 0.1 part, also
It is when saying that water-solubility rare-earth salt compounds are less, without additive effect, epithelium corrosion resistance and adhesion may decline；If
When the parts by weight of rare earth element are more than 1.5 parts, that is to say, that when water solubility compound containing rare earth salts is more, aqueous treating fluid
Stability can be deteriorated, and may influence the quality of galvanized steel sheet surface processing.
The method that the present invention provides galvanized steel plain sheet of the manufacture with excellent machining property, corrosion resistance and paintable, steel plate are dry
Dry temperature is between 80-180 DEG C, if being less than 80 DEG C, epithelium crosslinking is not enough, and may be caused under epithelium properties
Drop, if being higher than 180 DEG C, constituent part performance change in treatment fluid may influence film-formation result.
The surface conditioning agent of the present invention is coated on galvanized steel sheet surface, and thickness of dry film is micro- less than 2 between 2-4 microns
Meter Shi may result in punch process, resistance to acid and alkali and wear resistance and decline, leather film thickness is more than 4 since epithelium is than relatively thin
When micron, the surface treatment cost of unit area can be increased.
The present invention does not limit the heat drying method of the aqueous surface-treating agent coated on galvanized steel sheet surface particularly
System, can be Hot-blast Heating, sensing heating, infrared heating etc..The present invention is to size, shape of galvanized steel plain sheet etc. without special
Limitation.
Compared with prior art, beneficial effects of the present invention：
1) of the invention reduce to the greatest extent can be with the group of acid-base reaction, such as ester in waterborne cation polyurethane compound resin
Base, so that the epithelium formed has excellent resistance to acid and alkali.
2) in complex type organic silicon alkane coupling agent of the invention, by double organic alkane coupling agent and single organo silane coupling agent
To carry out the prepolymerization of part, the organic silane compound of synthesis can reinforce epithelium Z-direction crosslinking degree, to make
Epithelium wear resistance improves, corrosion resistance enhancing.
3) reactive group in surface modification high-density polyethylene particle of the invention can be with organosilicon in treatment fluid
Alkane coupling agent reacts to each other to form covalent key connection, can not only reinforce high density polyethylene (HDPE) particle and epithelium adhesion strength, also
High density polyethylene (HDPE) particle can be held onto, it, can to ensure that high density polyethylene (HDPE) particle can be dispersed in epithelium
Excellent wear resistance is provided in the whole thickness direction of epithelium, improves epithelium punch process and wear resistance.
4) present invention is grafted hydrophily reactive group in lamella surface of graphene oxide, improves graphene oxide in aqueous table
Stably dispersing coefficient in surface treatment agent system, enhances graphene oxide and the Compositional type in aqueous surface-treating agent system is organic
The chemical reaction of silane coupling agent or waterborne cation polyurethane compound resin, to improve graphene oxide and other components
Boundary strength, oxidation graphene act on the corrosion resistance of epithelium and the raising of wear resistance.
5) aqueous surface-treating agent of the invention is free of chromium, is environment-friendly type surface conditioning agent, and surface is carried out to galvanized steel plain sheet
After processing, galvanized steel plain sheet has excellent surface abrasion resistance, corrosion resistance and resistance to acid and alkali.
Description of the drawings
Fig. 1 is the double organic alkane coupling agent structural schematic diagram used in 5-8 of the embodiment of the present invention.
Fig. 2 is dispersion schematic diagram of the surface-functionalized graphene oxide used in the present invention in epithelium.
Specific implementation mode
Environmentally friendly surface conditioning agent to of the present invention for galvanized steel plain sheet, zinc-plated below in conjunction with specific embodiments
The manufacturing method of steel plate and galvanized steel plain sheet makes further explanation, however, the explanation and illustration is not to the present invention's
Technical solution constitutes improper restriction.
Embodiment 1-8 and comparative example 1-3
The base material of embodiment 1-8 and comparative example 1-3 are all made of the galvanized steel plain sheet of 0.5mm, zinc layer weight 60/60g/m2,
Basicity degreasing agent (pH in first being used to surface of steel plate：9~10) cleaning showers are carried out, are then cleaned with pure water, it is residual to remove surface
The alkaline components deposited will be coated in galvanized steel sheet surface for the environmentally friendly surface conditioning agent of galvanized steel plain sheet, be carried out at 80-180 DEG C
It is dry, to form the composite film that thickness is 2-4 microns in galvanized steel sheet surface.
Table 1 lists each component in the environmentally friendly surface conditioning agent for galvanized steel plain sheet in embodiment 1-8 and comparative example 1-3
Parts by weight.
Fig. 1 is double organic oxygen alkane (1,2- bis- second methoxyl group silicon substrate ethane) structural schematic diagram, it can be seen that 1,2- bis- second
The methoxyl group silicon substrate ethane alkoxy grp (- OMe groups) that there are 6 for reaction, can enhance double organic alkane coupling agent with
The ability of chemical bonding between metal substrate or other components reaches and strengthens epithelium adhesive force and corrosion proof purpose.
Table 2 lists embodiment 1-8 and drying temperature in comparative example 1-3 and is formed coated on galvanized steel sheet surface
Composite film thickness.
Fig. 2 is distribution schematic diagram of the surface-functionalized graphene oxide in epithelium, it can be seen that the oxidation of lamellar structure
Graphene uniform is dispersed in inside epithelium, and when Korrosionsmedium is to epithelium internal penetration, graphene oxide layer can increase
The permeation pathway of Korrosionsmedium plays the role of excellent physical protection, to increase substantially the corrosion resistance of epithelium.
It will be after the environmentally friendly surface conditioning agent coating for galvanized steel plain sheet in above-described embodiment 1-8 and comparative example 1-3
Galvanized steel plain sheet is according to after the regulation sampling of following test mode and being tested, evaluation its properties to be obtained
Test data is listed in Table 3 below.Wherein, the test for evaluating its various performance parameters is as follows：
1) tablet corrosion resistance：
Salt spray test, testing standard ASTMB117 are carried out to tablet, test period is 120 hours, evaluation criterion：
◎：White rust area occupation ratio is less than 5%
○：White rust area occupation ratio is more than 5% and is less than 10%
Δ：White rust area occupation ratio is more than 10% and is less than 50%
×：White rust area occupation ratio is more than 50%
2) corrosion resistance after being molded：
8mm cuppings are carried out using Sven-Gan Eriksson cupping instrument, salt spray test, testing standard ASTM are carried out to cupping position
B117, test period are 72 hours, evaluation criterion：
◎：Cupping position white rust area occupation ratio is less than 5%
○：Cupping position white rust area occupation ratio is more than 5% and is less than 10%
Δ：Cupping position white rust area occupation ratio is more than 10% and is less than 50%
×：Cupping position white rust area occupation ratio is more than 50%
3) corrosion resistance after alkali cleaning：
Basicity degreasing agent (pH in use：It 9-11) is cleaned, is sprayed 3 minutes at a temperature of 50 DEG C, to model after cleaning
Salt spray test is carried out, testing standard is ASTM B117, and test period is 240 hours, evaluation criterion：
◎：White rust area occupation ratio is less than 5%
○：White rust area occupation ratio is more than 5% and is less than 10%
Δ：White rust area occupation ratio is more than 10% and is less than 50%
×：White rust area occupation ratio is more than 50%
4) punching formation property：
Use bead method sample preparation.Experiment condition：Pressure 3KN under fixed pearl, pressure head diameter 9.6mm, drawing speed
200mm/min, evaluation criterion：
◎：Appearance is unchanged
○：The a small amount of stain of appearance
Δ：The more apparent blackstreak of appearance
×：Appearance blacks comprehensively
5) wear resistance：
Using rubber abrasion method, 500g, stroke distances 20mm, speed 300mm/min are loaded, repeated wear 50 times is commented
Price card is accurate：
◎：Epithelium is unchanged
○：Epithelium abrades on a small quantity
Δ：Epithelium many places abrade
×：Epithelium is completely fallen off
6) alkali resistance：
10min is impregnated in a concentration of 1% room temperature NaOH solution, is rinsed with water the change of rear visually observation appearance
Change, evaluation criterion：
◎：Appearance is unchanged
○：Appearance slight trace
Δ：The apparent albefaction of appearance and epithelium are partly dissolved
×：Epithelium is completely dissolved
7) acid resistance：
10min is impregnated in a concentration of 1% room temperature HCl solution, is rinsed with water the variation of rear visually observation appearance,
Evaluation criterion：
◎：Appearance is unchanged
○：Appearance slight trace
Δ：The apparent albefaction of appearance and epithelium are partly dissolved
×：Epithelium is completely dissolved
8) paintable：
After the galvanized steel plain sheet that surface treated is crossed carries out application according to the following conditions, painting adhesion test, examination are carried out
Test condition：
1. alkyd system white coating (Shanghai Chenhua Paint MFG. Co.'s product, the trade mark：A-09), 22# bar coatings, baking condition：140
DEG C baking 40 minutes；
2. epoxide powder coating (Akzo Nobel N.V.'s product, the trade mark：EA05BH), 70-80 microns of layer thickness of dusting,
Baking condition：200 DEG C are toasted 10 minutes；
After coating above-mentioned two coating, 100 small lattice, size 1mm are drawn in film coated surface using cutter2, depth
Paint film layer should be drawn to reach surface of steel plate.After being removed using cellotape, the residual lattice number of paint film is observed, residual lattice number is got over
It is more, illustrate that steel plate can be more excellent for the paintable of alkyd system white coating or epoxide powder coating.
Table 3 is listed by galvanized steel plain sheet takes after the coating of environmentally friendly surface conditioning agent in embodiment 1-8 and comparative example 1-3
Sample after tested after various performance parameters.
As can be seen from Table 3, using the galvanized steel plain sheet after the coating of environmentally friendly surface conditioning agent in embodiment 1-8 by upper
After stating every test, evaluation result is " ◎ " and "○", and its paintable is also preferable, illustrates to be coated with ring of the present invention
The galvanized steel plain sheet of water-retaining property surface conditioning agent all have excellent or good corrosion resistance (after tablet, molding and after alkali cleaning),
The comprehensive performances such as processability, wear resistance, resistance to acid and alkali and paintable.
It can know in conjunction with table 1 and table 3, compared to embodiment 1-8, due to not having in the environmentally friendly surface conditioning agent of comparative example 1
There is surface-functionalized graphene, and the parts by weight of polyurethane compound resin are in lower limit, therefore, is applied by the environmental protection surface conditioning agent
The corrosion resistance of galvanized steel plain sheet after covering, punch process and wear resistance are poor.In addition, due to the environmentally friendly surface of comparative example 2
The parts by weight of inorganic agent solid lubrication particle are less and the parts by weight of phosphorus-containing compound are in the upper limit, so, by the environmental protection surface
The corrosion resistance of epithelium of galvanized steel plain sheet after inorganic agent coating, processability and wear resistance are poor.In addition, the environmental protection of comparative example 3
The parts by weight of metal-rare-earth salt compound in surface conditioning agent are less, as a result, the plating after environmental protection surface conditioning agent coating
The corrosion resistance and alkali resistance of zinc steel plate are poor.
As it can be seen that the galvanized steel plain sheet of the present invention has excellent surface wear resistance, corrosion resistance and resistance to acid and alkali, meet multiple necks
Domain user is to the environmental protection of galvanized steel plain sheet, the requirement of surface abrasion resistance damage, punch process and defatting-bonderizing.
It should be noted that the above list is only specific embodiments of the present invention, it is clear that the present invention is not limited to above real
Example is applied, there are many similar variations therewith.If those skilled in the art directly exported from present disclosure or
All deformations associated, are within the scope of protection of the invention.
Metatitanic acid；F1 is orthophosphoric acid, and F2 is ammonium phosphate；G1 is ammonium ceric nitrate, and G2 is lanthanum nitrate, and G3 is potassium chlorate fluozirconate.
Table 2
| Serial number | Drying temperature (DEG C) | Composite film thickness (μm) |
| Embodiment 1 | 160 | 2.5 |
| Embodiment 2 | 140 | 3 |
| Embodiment 3 | 120 | 3.5 |
| Embodiment 4 | 100 | 4 |
| Embodiment 5 | 120 | 2 |
| Embodiment 6 | 80 | 3 |
| Embodiment 7 | 180 | 3.5 |
| Embodiment 8 | 150 | 2.5 |
| Comparative example 1 | 80 | 3 |
| Comparative example 2 | 100 | 2.5 |
| Comparative example 3 | 180 | 1.0 |
Claims (27)
1. the galvanized steel plain sheet with excellent surface wear resistance, corrosion resistance and resistance to acid and alkali, surface cover Organic-inorganic composite
Epithelium, the epithelium contain：
A) waterborne cation polyurethane compound resin, the parts by weight in epithelium are 30-50 parts；The waterborne cation polyurethane
Compound resin is by the one or more and poly- ammonia in polytetrahydrofuran ether, polyacrylate or poly- perfluoroalkyl acrylate
Ester performed polymer is copolymerized, relative molecular weight 80000-150000；
B) complex type organic silicon alkane coupling agent, the parts by weight in epithelium are 20-45 parts；
The complex type organic silicon alkane coupling agent is that at least one double organic alkane coupling agent and at least one single organosilan are even
Join the mixture of agent；The double organic alkane coupling agent contains bridging structure, the double organic alkane coupling agent and single organosilan
The weight ratio of coupling agent is 0.3-2；
C) composite lubricated particle, the parts by weight in epithelium are 15-25 parts；The composite lubricated particle includes polytetrafluoroethylene (PTFE) grain
Son and surface modification high-density polyethylene particle；
D the parts by weight of) graphene oxide water solution, wherein graphene oxide in epithelium are 0.1-0.5 parts；The oxidation stone
In black aqueous solution, the mass fraction of graphene oxide is 1-5%；
E the parts by weight of) water-soluble fluorine-containing compound, wherein fluorine element in epithelium are 0.5-1.5 parts；
F) water-soluble phosphorus-containing compound, wherein parts by weight of the P elements in epithelium are 1-2 parts；
G) water-solubility rare-earth salt compounds, parts by weight of the rare earth elements in epithelium are 0.1-1.5 parts.
2. the galvanized steel plain sheet according to claim 1 with excellent surface wear resistance, corrosion resistance and resistance to acid and alkali, special
Sign is that the Organic-inorganic composite protective film is single layer structure, and film thickness range is 2-4 microns.
3. the galvanized steel plain sheet according to claim 1 with excellent surface wear resistance, corrosion resistance and resistance to acid and alkali, special
Sign is that parts by weight of the waterborne cation polyurethane compound resin (A) in epithelium are 35-45 parts.
4. the galvanized steel plain sheet according to claim 1 with excellent surface wear resistance, corrosion resistance and resistance to acid and alkali, special
Sign is, when preparing waterborne cation polyurethane compound resin (A), the base polyurethane prepolymer for use as is by the polyalcohols without ester group
Compound reacts acquisition with aliphatic isocyanates or aromatic isocyanate compound.
5. the galvanized steel plain sheet according to claim 1 with excellent surface wear resistance, corrosion resistance and resistance to acid and alkali, special
Sign is, in the complex type organic silicon alkane coupling agent (B), the bridging structure of the double organic alkane coupling agent is by 2-4
Methylene, amino or sulfydryl composition.
6. the galvanized steel plain sheet according to claim 1 with excellent surface wear resistance, corrosion resistance and resistance to acid and alkali, special
Sign is, in the complex type organic silicon alkane coupling agent (B), at least contains one in the molecule of single organo silane coupling agent
It is a have reactive group, it is described have reactive group be amino, epoxy group or vinyl.
7. the galvanized steel plain sheet according to claim 1 with excellent surface wear resistance, corrosion resistance and resistance to acid and alkali, special
Sign is that the weight ratio of the complex type organic silicon alkane coupling agent (B) and waterborne cation polyurethane compound resin (A) is
0.5-1.5。
8. the galvanized steel plain sheet according to claim 1 with excellent surface wear resistance, corrosion resistance and resistance to acid and alkali, special
Sign is, the weight ratio of polytetrafluoroethylparticle particle and surface modification high-density polyethylene particle in the composite lubricated particle (C)
For 1-3；The polytetrafluoroethylparticle particle is 0.3-0.8 microns a diameter of, and the surface modification high-density polyethylene particle is straight
Diameter is 3-5 microns.
9. the galvanized steel plain sheet according to claim 8 with excellent surface wear resistance, corrosion resistance and resistance to acid and alkali, special
Sign is that the surface modification high-density polyethylene particle surface is grafted with reactive group, and the reactive group is
It is one or more in amino, hydroxyl, carboxyl, epoxy group or carbamate groups.
10. the galvanized steel plain sheet according to claim 1 with excellent surface wear resistance, corrosion resistance and resistance to acid and alkali,
It is characterized in that, the graphene oxide water solution (D) is surface-functionalized graphene oxide water solution, and described is surface-functionalized
Graphene oxide refers to being grafted with hydrophily reactive group in surface of graphene oxide, the hydrophily reactive group be amino,
It is one or more in hydroxyl and carboxyl.
11. the galvanized steel with excellent surface wear resistance, corrosion resistance and resistance to acid and alkali according to claim 1 or 10
Plate, which is characterized in that in the graphene oxide water solution (D), the graphene oxide is single layer or multilayer, works as oxidation
When graphene is multilayer, piece layer number is 5 layers or less.
12. the galvanized steel plain sheet according to claim 1 with excellent surface wear resistance, corrosion resistance and resistance to acid and alkali,
It is characterized in that, the water-soluble fluorine-containing compound (E) is fluorine-containing metallic salt or fluorine-containing acids.
13. the galvanized steel plain sheet according to claim 1 with excellent surface wear resistance, corrosion resistance and resistance to acid and alkali,
It is characterized in that, the water-soluble fluorine-containing compound (E) is sodium fluoride, ammonium titanium fluoride, prodan, hexafluorotitanic acid and fluosilicic acid
In it is one or more.
14. the galvanized steel plain sheet according to claim 1 with excellent surface wear resistance, corrosion resistance and resistance to acid and alkali,
It is characterized in that, the water-soluble phosphorus-containing compound (F) is phosphoric acid salt or phosphorous acids.
15. the galvanized steel plain sheet according to claim 1 with excellent surface wear resistance, corrosion resistance and resistance to acid and alkali,
Be characterized in that, the water-soluble phosphorus-containing compound (F) be orthophosphoric acid, pyrophosphoric acid, tripolyphosphate, three poly-metaphosphoric acids, ammonium phosphate,
It is one or more in aluminium triphosphate and ammonium polyphosphate.
16. the galvanized steel plain sheet according to claim 1 with excellent surface wear resistance, corrosion resistance and resistance to acid and alkali,
It is characterized in that, the water-solubility rare-earth salt compounds (G) are at least one in rare earth cerium salt, La-salt and rare earth zirconates
Kind.
17. the galvanized steel plain sheet according to claim 16 with excellent surface wear resistance, corrosion resistance and resistance to acid and alkali,
It is characterized in that, the rare earth cerium salt is one or more in cerous nitrate, cerous sulfate, fluorine-containing cerium salt, cerium ammonium compound salt；Rare earth
Lanthanum salt is one or more in lanthanum chloride, lanthanum sulfate and lanthanum nitrate；Rare earth zirconates is in potassium chlorate fluozirconate, zirconium nitrate and zirconium sulfate
It is one or more.
18. as claim 1-17 any one of them has the zinc-plated of excellent surface wear resistance, corrosion resistance and resistance to acid and alkali
Steel plate aqueous surface-treating agent, total solid part contains following component in aqueous solution：
A) waterborne cation polyurethane compound resin, the parts by weight in epithelium are 30-50 parts；The waterborne cation polyurethane
Compound resin is by one or more pre- with polyurethane in polytetrahydrofuran ether, polyacrylate or poly- perfluoroalkyl acrylate
Aggressiveness is copolymerized, relative molecular weight 80000-150000；
B) complex type organic silicon alkane coupling agent, the parts by weight in epithelium are 20-45 parts；
The complex type organic silicon alkane coupling is at least one double organic alkane coupling agent and at least one single organosilan coupling
The mixture of agent；The double organic alkane coupling agent contains bridging structure, and the double organic alkane coupling agent and single organosilan are even
The weight ratio for joining agent is 0.3-2；
C) composite lubricated particle, the parts by weight in epithelium are 15-25 parts；The composite lubricated particle includes polytetrafluoroethylene (PTFE) grain
Son and surface modification high-density polyethylene particle；
D the parts by weight of) graphene oxide water solution, wherein graphene oxide in epithelium are 0.1-0.5 parts；The oxidation stone
In black aqueous solution, the mass fraction of graphene oxide is 1-5%；
E the parts by weight of) water-soluble fluorine-containing compound, wherein fluorine element in epithelium are 0.5-1.5 parts；
F) water-soluble phosphorus-containing compound, wherein parts by weight of the P elements in epithelium are 1-2 parts；
G) water-solubility rare-earth salt compounds, parts by weight of the rare earth elements in epithelium are 0.1-1.5 parts.
19. the galvanized steel plain sheet water with excellent surface wear resistance, corrosion resistance and resistance to acid and alkali as claimed in claim 18
Property surface conditioning agent, which is characterized in that parts by weight of the waterborne cation polyurethane compound resin (A) in epithelium are
35-45 parts.
20. the galvanized steel plain sheet water with excellent surface wear resistance, corrosion resistance and resistance to acid and alkali as claimed in claim 18
Property surface conditioning agent, which is characterized in that when preparing waterborne cation polyurethane compound resin (A), the base polyurethane prepolymer for use as
It is to react acquisition with aliphatic isocyanates or aromatic isocyanate compound by the polyol compounds without containing ester group.
21. the galvanized steel plain sheet with excellent surface wear resistance, corrosion resistance and resistance to acid and alkali stated such as claim 18 is with aqueous
Surface conditioning agent, which is characterized in that in the complex type organic silicon alkane coupling agent (B), the double organic alkane coupling agent
Bridging structure is made of 2-4 methylene, amino or sulfydryl；At least contain one in the molecule of single organo silane coupling agent
It is a have reactive group, it is described have reactive group be amino, epoxy group or vinyl.
22. the galvanized steel plain sheet water with excellent surface wear resistance, corrosion resistance and resistance to acid and alkali as claimed in claim 18
Property surface conditioning agent, which is characterized in that the complex type organic silicon alkane coupling agent (B) and the compound tree of waterborne cation polyurethane
The weight ratio of fat (A) is 0.5-1.5.
23. the galvanized steel plain sheet water with excellent surface wear resistance, corrosion resistance and resistance to acid and alkali as claimed in claim 18
Property surface conditioning agent, which is characterized in that polytetrafluoroethylparticle particle and surface modification high-density are poly- in the composite lubricated particle (C)
The weight ratio of beta particles is 1-3；The polytetrafluoroethylparticle particle is 0.3-0.8 microns a diameter of, and the surface is modified high
Density polyethylene particles are 3-5 microns a diameter of.
24. the galvanized steel plain sheet water with excellent surface wear resistance, corrosion resistance and resistance to acid and alkali as claimed in claim 23
Property surface conditioning agent, which is characterized in that the surface modification high-density polyethylene particle surface is grafted with reactive group, institute
The reactive group stated is one or more in amino, hydroxyl, carboxyl, epoxy group or carbamate groups.
25. the galvanized steel plain sheet water with excellent surface wear resistance, corrosion resistance and resistance to acid and alkali as claimed in claim 18
Property surface conditioning agent, which is characterized in that the graphene oxide water solution (D) be surface-functionalized graphene oxide water solution,
The surface-functionalized graphene oxide refers to being grafted with hydrophily reactive group, the hydrophily in surface of graphene oxide
Reactive group is one or more in amino, hydroxyl and carboxyl.
26. as claim 18-25 any one of them has the zinc-plated of excellent surface wear resistance, corrosion resistance and resistance to acid and alkali
Steel plate aqueous surface-treating agent, which is characterized in that the water-soluble fluorine-containing compound (E) is fluorine-containing metallic salt or fluorine-containing
Acids, the water-soluble phosphorus-containing compound (F) are phosphoric acid salt or phosphorous acids, the water-solubility rare-earth salt compounds
(G) it is at least one of rare earth cerium salt, La-salt and rare earth zirconates.
27. a kind of plating with excellent surface wear resistance, corrosion resistance and resistance to acid and alkali as described in claim 1-14 is any
Any one of the claim 15-23 aqueous surface-treating agents are coated to table by the preparation method of zinc steel plate by a roller coating
Face, and be dried between 80-180 DEG C, make thickness of dry film at 2-4 microns.
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| CN201510705304.2A CN105255338B (en) | 2015-10-27 | 2015-10-27 | Galvanized steel plain sheet with excellent surface wear resistance, corrosion resistance and resistance to acid and alkali and aqueous surface-treating agent |
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| CN201510705304.2A CN105255338B (en) | 2015-10-27 | 2015-10-27 | Galvanized steel plain sheet with excellent surface wear resistance, corrosion resistance and resistance to acid and alkali and aqueous surface-treating agent |
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| CN105255338B true CN105255338B (en) | 2018-10-02 |
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