CN105255338A - Galvanized steel sheet excellent in surface abrasion resistance, corrosion resistance and acid and base resistance and water-based surface treating agent - Google Patents
Galvanized steel sheet excellent in surface abrasion resistance, corrosion resistance and acid and base resistance and water-based surface treating agent Download PDFInfo
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- CN105255338A CN105255338A CN201510705304.2A CN201510705304A CN105255338A CN 105255338 A CN105255338 A CN 105255338A CN 201510705304 A CN201510705304 A CN 201510705304A CN 105255338 A CN105255338 A CN 105255338A
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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
The invention relates to a galvanized steel sheet excellent in surface abrasion resistance, corrosion resistance and acid and base resistance and a water-based surface treating agent. The surface of a galvanized steel sheet is coated with the surface treating agent in a solidified mode, wherein the surface treating agent includes water-based positive ion polyurethane composite resin, compound organic silane coupling agents containing bis-organic silane coupling agents and mono-organic silane coupling agents, compound lubrication particles containing teflon-surface modification high-density polyethylene particles, oxidized graphene, water-soluble fluorine-containing compounds, water-soluble phosphorous compounds, water-soluble rare earth salt compounds and other components, and therefore the surface treatment galvanized steel sheet excellent in surface abrasion resistance, corrosion resistance and acid and base resistance is obtained. Meanwhile, the surface treatment galvanized steel sheet has good resistance, such as solvent resistance, to all kinds of chemical media.
Description
Technical field
The invention belongs to technical field of metal material surface treatment, be specifically related to a kind of steel plate galvanized and the aqueous surface-treating agent with excellent surface wearability, solidity to corrosion and resistance to acids and bases.
Background technology
Steel plate galvanized is widely used in the every field such as automobile, household electrical appliances and building, how to use as component such as automobile, household electrical appliance, OA goods.But in steel plate galvanized storage transport and processing use procedure, there is multiple key issue to need to pay close attention to, such as, for preventing steel plate galvanized, corrosion occurs in transport and storage process and produce white rust, when producing steel plate, will slushing oil be coated with; For reducing the friction in impact briquetting process between mould and sheet material, prevent sheet material from ftractureing and the scratch of surperficial zinc layers, to mould apply oil, will carry out cleaning by degreasing again after shaping when part punching is shaping, grease-removing agent can be divided into solvent-borne type grease-removing agent and alkaline defatting agent.
In the whole accumulating of steel plate galvanized, punching course, the use of slushing oil, lubricating oil and grease-removing agent is all disadvantageous to environment and production cost.In order to improve solidity to corrosion and processing forming, the method in past mainly carries out chromic acid passivation surface treatment to steel plate galvanized, and this method can improve steel plate solidity to corrosion, but improves limited to its processing forming and other resistances; Or coating (is generally low surface energy polymeric containing solid lubrication auxiliary agent again on the basis of chromating, as polyolefine and tetrafluoroethylene) organic resin, to take into account anti-corrosion and lubricant effect, meet the requirement that steel plate is anti-corrosion and shaping, but, the surface treated steel plate that these class methods of this employing are produced is all containing chromium element, and in use chromium element precipitation can work the mischief to human body and environment.
Surface treatment steel plate galvanized is when OA goods or vending machine industry appliance naked as inside, meeting and paper, beverage bottle or the contact friction repeatedly of food casing bag, for prevent surface of steel plate with external substance multiple-contact process in be worn, there is the problem that the follow-up solidity to corrosion of steel plate significantly declines.Meanwhile, when the industry such as Electric Appliance Cabinet and cabinet uses as outer hull, also often there is phase mutual friction, cause surface blackening to affect outward appearance in surface treatment steel plate galvanized in housing transportation.Above situation all requires that galvanized steel sheet surface has good wearability.
For improving galvanized steel sheet surface wearability, normally adopting the production technique of two-step approach, carrying out chromating at surface of steel plate, play the effect strengthening coating adhesion.And then the polymkeric substance epithelium of coating thicker (being greater than 5 microns), play the effect of strengthening surface wearability.But the softening temperature of polymkeric substance epithelium is lower usually, in continuous punching process, mould heating easily causes epithelium softening damaged.Meanwhile, along with the appearance of environmental protection instruction, containing chromium process steel plate galvanized also gradually replace by environmentally friendly machine.
Secondly, in steel plate galvanized use procedure, otch is antirust is issues that need special attention.After degreasing, bonderizing is that the one that a lot of industry adopts at present commonly uses the antirust care method of otch, specific as follows: after punch process, short period of time alkalescence degreasing first to be carried out to punching parts and then carry out bonderizing, part incision site is made to generate one deck phosphatize phosphate coat, this phosphatize phosphate coat plays a protective role to otch, but, alkali (alkaline defatting agent solution in this treating processes, the general 9-11 of pH value) and acid (Phosphating Solution, the general 3-4 of pH value) all the surperficial epithelium of effects on surface process steel plate galvanized can play destruction, thus affect the wearability of epithelium and follow-up corrosion resisting property, therefore the resistance to acids and bases of such Application Areas effects on surface process steel plate galvanized requires high.
Chinese patent CN104449154A provides a kind of aqueous chromium-free fingerprint-resistant coating for steel plate galvanized, and the steel plate after this coating process has excellent corrosion resistance and alkali resistance degreasing.But the surface abrasion resistance of not mentioned steel plate galvanized after this coating process, processing forming and acid resistance in this patent.But, in OA goods or vending machine industry, surface of steel plate can with paper, beverage bottle or the contact friction repeatedly of food casing bag, the surperficial epithelium of this surface treated steel plate may easily with external substance repeatedly friction process in be worn, there is the problem that steel plate solidity to corrosion significantly declines.
Chinese patent CN102272253A provides a kind of surface of steel plate process resin combination containing Graphene and utilizes the surface treated steel plate of said composition.This resin combination, by binder resin, Graphene and solvent composition, utilizes the steel plate of this resin combination process to have good electroconductibility, solidity to corrosion, tack and processibility.
Graphene is a kind of novel material of the two-dimension single layer sheet structure having carbon atom to form, and can be layering and cover matrix surface formation dense coating, play excellent physical isolation effect.Dispersed graphene sheet layer in the coating can increase the permeation pathway that corrosive medium infiltrates into base material, thus corrosive medium can be stoped for a long time to the destruction of base material, effectively improves the corrosion resistance nature of coating.Simultaneously, be carbon-to-carbon covalent linkage between each atom of Graphene to connect, lamella and sheet interlayer are Van der Waals force, therefore sheet interlayer easily slides mutually, there is excellent mechanical property and self-lubricating property, therefore Graphene can play again the effect strengthening wearability, but, due to graphene sheet layer and sheet interlayer Van der Waals force stronger, Graphene in use monolithic graphite alkene sheet interlayer easily occur lamella reunite, and in water-based system, form comparatively macro aggregate, and precipitation is separated out fast in water-based system, thus do not have the object of increase system physical strength and wearability.
Summary of the invention
The object of the present invention is to provide a kind of steel plate galvanized with excellent surface wearability, solidity to corrosion and resistance to acids and bases, meet that multiple field user damages the environmental protection of steel plate galvanized, surface abrasion resistance, the requirement of punch process and defatting-bonderizing, this surface treatment steel plate galvanized also has the good resistance of all kinds of chemical mediator as solvent resistance etc.
Specifically, after surface abrasion resistance comprises surface of steel plate oilness, punch process under outward appearance and high/low temperature steel ball repeatedly rub after outward appearance; Solidity to corrosion comprises the solidity to corrosion after dull and stereotyped solidity to corrosion, shaping rear solidity to corrosion and defatting-bonderizing; Resistance to acids and bases comprises acid resistance, alkali resistance and resistance to defatting-bonderizing.
Through arduous research, find the surface treatment steel plate galvanized by being formed at the surface treatment agent of galvanized steel sheet surface coating solidification containing compositions such as waterborne cation polyurethane compound resin, the complex type organic silicon alkane coupling agent comprising double organic alkane coupling agent and single organo silane coupling agent, the composite lubricated particle comprising tetrafluoroethylene-surface modification high density polyethylene(HDPE) particle, graphene oxide, water-soluble fluorine-containing compound, water-soluble P contained compound and water-solubility rare-earth salt compounds, can achieve the above object, thus complete the present invention.
Meanwhile, the present invention also provides a kind of and can stablize the environment-friendly type aqueous surface treatment agent manufacturing above-mentioned surface treatment steel plate galvanized.
Technical scheme of the present invention is as follows:
Have a steel plate galvanized for excellent surface wearability, solidity to corrosion and resistance to acids and bases, its surface coverage has Organic-inorganic composite epithelium, and this epithelium contains:
A) waterborne cation polyurethane compound resin, the weight part in epithelium is 30-50 part;
Described waterborne cation polyurethane compound resin is formed by one or more in PTMG, polyacrylic ester or poly-perfluoroalkyl acrylate and base polyurethane prepolymer for use as copolymerization, and relative molecular weight is 80000-150000;
B) complex type organic silicon alkane coupling agent, the weight part in epithelium is 20-45 part;
The coupling of described complex type organic silicon alkane is the mixture of at least one double organic alkane coupling agent and at least one list organo silane coupling agent; Described double organic alkane coupling agent is containing bridging structure, and the weight ratio of described double organic alkane coupling agent and single organo silane coupling agent is 0.3-2;
C) composite lubricated particle, the weight part in epithelium is 15-25 part; Described composite lubricated particle comprises polytetrafluoroethylparticle particle and surface modification high density polyethylene(HDPE) particle;
D) graphene oxide water solution, wherein the weight part of graphene oxide in epithelium is 0.1-0.5 part; In described graphene oxide water solution, the massfraction of graphene oxide is 1-5%;
E) water-soluble fluorine-containing compound, wherein the weight part of fluorine element in epithelium is 0.5-1.5 part;
F) water-soluble P contained compound, wherein the weight part of phosphoric in epithelium is 1-2 part;
G) water-solubility rare-earth salt compounds, the weight part of its rare earth elements in epithelium is 0.1-1.5 part.
Above-mentioned have in the steel plate galvanized of excellent surface wearability, solidity to corrosion and resistance to acids and bases:
Described Organic-inorganic composite protective membrane is single layer structure, and its film thickness range is 2-4 micron.
Further, described waterborne cation polyurethane compound resin (A) is by being selected from PTMG, at least one in polyacrylic ester or poly-perfluoroalkyl acrylate and base polyurethane prepolymer for use as copolymerization form, wherein, described base polyurethane prepolymer for use as is by polytetrahydrofuran diol, Polyoxyethylene glycol or polycaprolactone glycol etc. do not react containing the polyol compounds of ester group and aliphatic isocyanates or aromatic isocyanate compound and obtain, the relative molecular weight of described waterborne cation polyurethane compound resin is at 80000-150000, weight part in epithelium is 30-50 part, preferred 35-45 part.
In described complex type organic silicon alkane coupling agent (B), the bridging structure of described double organic alkane coupling agent is made up of 2-4 methylene radical, amino or sulfydryl, at least containing one, there is reactive group in the molecule of described single organo silane coupling agent, described have reactive group for amino, epoxy group(ing) or vinyl, and described complex type organic silicon alkane coupling agent (B) and the weight ratio of waterborne cation polyurethane compound resin (A) are 0.5-1.5.
In described composite lubricated particle (C), the weight ratio of polytetrafluoroethylparticle particle and surface modification high density polyethylene(HDPE) particle is 1-3, described polytetrafluoroethylparticle particle diameter (middle several diameter) is 0.3-0.8 micron, described surface modification high density polyethylene(HDPE) particle dia (middle several diameter) is 3-5 micron, described surface modification high density polyethylene(HDPE) particle surface is grafted with reactive group, and described reactive group is one or more in amino, hydroxyl, carboxyl, epoxy group(ing) or carbamate groups.
In described graphene oxide water solution (D), described graphene oxide is individual layer or multilayer, and when graphene oxide is multilayer, lamella quantity is less than 5 layers.
Further, described graphene oxide water solution (D) is surface-functionalized graphene oxide water solution, described surface-functionalized graphene oxide refers to and is grafted with wetting ability reactive group in surface of graphene oxide, and described wetting ability reactive group is one or more in amino, hydroxyl and carboxyl.
Described water-soluble fluorine-containing compound (E) is fluorine-containing metallic salt or fluorine-containing acids, and for example, water-soluble fluorine-containing compound can be one or more in Sodium Fluoride, ammonium titanium fluoride, Sodium Silicofluoride, hexafluorotitanic acid and silicofluoric acid.
Described water-soluble P contained compound (F) is phosphoric acid salt or phosphorous acids, for example, water-soluble P contained compound can be one or more in ortho-phosphoric acid, tetra-sodium, tripolyphosphate, trimerization metaphosphoric acid, ammonium phosphate, aluminium triphosphate and ammonium polyphosphate.
Described water-solubility rare-earth salt compounds (G) is cerium salt, at least one in La-salt and rare earth zirconates, for example, cerium salt can be cerous nitrate, cerous sulfate, also can be fluorine-containing cerium salt, or one or more in cerium ammonium compound salt; La-salt can be one or more in Lanthanum trichloride, lanthanum sulfat and lanthanum nitrate; Rare earth zirconates can be one or more in potassium chlorate fluozirconate, zirconium nitrate and zirconium sulfate.
Have a surface treating agent for galvanized steel sheet for excellent surface wearability, solidity to corrosion and resistance to acids and bases, in its aqueous solution, total solids part contains following composition:
A) waterborne cation polyurethane compound resin, the weight part in epithelium is 30-50 part; The relative molecular weight of described waterborne cation polyurethane compound resin is 80000-150000, is formed by one or more in PTMG, polyacrylic ester or poly-perfluoroalkyl acrylate and base polyurethane prepolymer for use as copolymerization;
B) complex type organic silicon alkane coupling agent, the weight part in epithelium is 20-45 part;
The coupling of described complex type organic silicon alkane is the mixture of at least one double organic alkane coupling agent and at least one list organo silane coupling agent; Described double organic alkane coupling agent is containing bridging structure, and the weight ratio of described double organic alkane coupling agent and single organo silane coupling agent is 0.3-2;
C) composite lubricated particle, the weight part in epithelium is 15-25 part; Described composite lubricated particle comprises polytetrafluoroethylparticle particle and surface modification high density polyethylene(HDPE) particle;
D) graphene oxide water solution, wherein the weight part of graphene oxide in epithelium is 0.1-0.5 part; In described graphene oxide water solution, the massfraction of graphene oxide is 1-5%;
E) water-soluble fluorine-containing compound, wherein the weight part of fluorine element in epithelium is 0.5-1.5 part;
F) water-soluble P contained compound, wherein the weight part of phosphoric in epithelium is 1-2 part;
G) water-solubility rare-earth salt compounds, the weight part of its rare earth elements in epithelium is 0.1-1.5 part.
Further, described waterborne cation polyurethane compound resin (A) is by being selected from PTMG, at least one in polyacrylic ester or poly-perfluoroalkyl acrylate and base polyurethane prepolymer for use as copolymerization form, wherein, described base polyurethane prepolymer for use as is by polytetrahydrofuran diol, Polyoxyethylene glycol or polycaprolactone glycol etc. do not react containing the polyol compounds of ester group and aliphatic isocyanates or aromatic isocyanate compound and obtain, the relative molecular weight of described urethane compound resin is at 80000-150000, weight part in epithelium is 30-50 part, preferred 35-45 part.
In described complex type organic silicon alkane coupling agent (B), the bridging structure of described double organic alkane coupling agent is made up of 2-4 methylene radical, amino or sulfydryl, at least containing one, there is reactive group in the molecule of described single organo silane coupling agent, described have reactive group for amino, epoxy group(ing) or vinyl, and described complex type organic silicon alkane coupling agent (B) and the weight ratio of waterborne cation polyurethane compound resin (A) are 0.5-1.5.
In described composite lubricated particle (C), the weight ratio of polytetrafluoroethylparticle particle and surface modification high density polyethylene(HDPE) particle is 1-3; Described polytetrafluoroethylparticle particle diameter (middle several diameter) is 0.3-0.8 micron, described surface modification high density polyethylene(HDPE) particle dia (middle several diameter) is 3-5 micron, described surface modification high density polyethylene(HDPE) particle surface is grafted with reactive group, and described reactive group is one or more in amino, hydroxyl, carboxyl, epoxy group(ing) or carbamate groups.
In described graphene oxide water solution (D), described graphene oxide is individual layer or multilayer, and when graphene oxide is multilayer, lamella quantity is less than 5 layers.
Further, described graphene oxide water solution (D) is surface-functionalized graphene oxide water solution, described surface-functionalized graphene oxide refers to and is grafted with wetting ability reactive group in surface of graphene oxide, and described wetting ability reactive group is one or more in amino, hydroxyl and carboxyl.
Described water-soluble fluorine-containing compound (E) is fluorine-containing metallic salt or fluorine-containing acids, and for example, water-soluble fluorine-containing compound can be one or more in Sodium Fluoride, ammonium titanium fluoride, Sodium Silicofluoride, hexafluorotitanic acid and silicofluoric acid.
Described water-soluble P contained compound (F) is phosphoric acid salt or phosphorous acids, for example, water-soluble P contained compound can be one or more in ortho-phosphoric acid, tetra-sodium, tripolyphosphate, trimerization metaphosphoric acid, ammonium phosphate, aluminium triphosphate and ammonium polyphosphate.
Described water-solubility rare-earth salt compounds (G) is cerium salt, at least one in La-salt and rare earth zirconates, for example, cerium salt can be cerous nitrate, cerous sulfate, also can be fluorine-containing cerium salt, or one or more in cerium ammonium compound salt; La-salt can be one or more in Lanthanum trichloride, lanthanum sulfat and lanthanum nitrate; Rare earth zirconates can be one or more in potassium chlorate fluozirconate, zirconium nitrate and zirconium sulfate.
A further object of the invention is to provide a kind of preparation method with the steel plate galvanized of excellent surface wearability, solidity to corrosion and resistance to acids and bases, by the component of described aqueous surface-treating agent by being dissolved or dispersed in water, form aqueous surface-treating agent, described aqueous surface-treating agent is coated to surface by a roller coat, and drying is carried out between 80-180 DEG C, make build at 2-4 micron.
The waterborne cation polyurethane compound resin that the present invention uses, containing cationic hydrophilic groups, can show as water-soluble, or form water-base resin by Forced Dispersion in water medium, therefore, it can be the aqueous solution, also can be aqueous dispersion type.
The present invention to reduce in waterborne cation polyurethane compound resin as far as possible can with the group of acid-base reaction, as ester group etc., to make the epithelium of formation, there is excellent resistance to acids and bases.Waterborne cation polyurethane compound resin used in the present invention is formed by one or more in PTMG, polyacrylic ester or poly-perfluoroalkyl acrylate and base polyurethane prepolymer for use as copolymerization, wherein, PTMG, polyacrylic ester or poly-perfluoroalkyl acrylate have good chemical resistance and physical and mechanical properties, acid-proof alkaline and the solvent resistance of epithelium can not only be strengthened, epithelial surfaces hardness can also be improved, thus strengthen the abrasion resistance properties of epithelium.In waterborne cation polyurethane compound resin of the present invention, its base polyurethane prepolymer for use as can be do not reacted containing the polyol compounds of ester group and aliphatic isocyanates or aromatic isocyanate compound by polytetrahydrofuran diol, Polyoxyethylene glycol or polycaprolactone glycol etc. to obtain, and does not adopt the polycarbonate polyalcohols containing ester group and polyester polyalcohols synthesis of polyurethane performed polymer.
Waterborne cation polyurethane compound resin used in the present invention, its relative molecular weight is in the scope of 80000-150000, if its relative molecular weight discontented 80000, the hardness of epithelium entirety is inadequate, thus the wearability of epithelium may be caused not enough; If its relative molecular weight is more than 150000, epithelium snappiness declines, unit elongation reduces, and when punch process, epithelium is not with substrate deformation, and materials processing may be caused bad.
Waterborne cation polyurethane compound resin used in the present invention, in epithelium, shared weight part is 30-50 part, if lower than 30 parts, the wearability of epithelium, punching formation property, solvent resistance and solidity to corrosion can reduce; If more than 50 parts, the resistance to acids and bases of epithelium may reduce, and preferred weight part is 35-45 part.
In complex type organic silicon alkane coupling agent of the present invention, double organic alkane coupling agent refers to there are two silane structure in same molecular structure, a molecule there are 6 alkoxy grps, it is the twice of common single organo silane coupling agent, double organic alkane coupling agent of the present invention contains bridging structure, its bridging structure can by 2-4 methylene radical, amino or sulfydryl forms, there is no particular limitation for other structures, for example, 1, the two silica-based ethane of trimethoxy of 2-, 1, the two silica-based ethane of second methoxyl group of 2-, two-(the silica-based propyl group of γ-triethoxy) tetrasulfide, two-[γ-(triethoxysilicane) propyl group]-disulphide, the similar constituents such as two-(the silica-based propyl group of γ-trimethoxy) amine can use, with use conventional single organo silane coupling agent unlike, having 6 in the double organic alkane coupling agent used in the present invention can for the alkoxy grp of reaction, double organic alkane coupling agent and the chemical bonding between metal substrate and other components can be strengthened, not only can improve the cross-linking density of epithelium, reach strengthening epithelium wearability and corrosion proof object, but also the sticking power of epithelium and metal substrate can be strengthened.
In complex type organic silicon alkane coupling agent of the present invention, at least containing one, there is reactive group in each molecule of the single organo silane coupling agent used, as amino, epoxy group(ing) or vinyl etc., there is no particular limitation for other structures, for example, the similar constituent such as 3-aminopropyl triethoxysilane, N-(2-aminoethyl) 3-aminopropyl trimethoxysilane, 3-epoxy group(ing) Trimethoxy silane, 2-(3,4-epoxy cyclohexane base) ethyl trimethoxy silane, vinyl silane triisopropoxide, vinyltriethoxysilane can use.
In complex type organic silicon alkane coupling agent of the present invention, after double organic alkane coupling agent and single organo silane coupling agent mix, both will carry out the prepolymerization of part, the organic silane compound of synthesis can strengthen the crosslinking degree of epithelium in Z-direction, thus epithelium wearability is improved, solidity to corrosion strengthens.In the organic silane compound simultaneously synthesized remaining active group can with metal substrate surface reaction, strengthen and the interface tack of metal substrate.In epithelium, the weight ratio of double organic alkane coupling agent and single organo silane coupling agent is preferably in the scope of 0.3-2, if lower than 0.3, when namely double organic alkane coupling agent is less, solidity to corrosion and the sticking power of epithelium are poor, in impact briquetting process, easily occur that epithelium comes off, and easily occurs corrosion in process under arms; If be greater than 2, when namely double organic alkane coupling agent is more, double organic alkane coupling agent not facile hydrolysis, easily causes treatment agent layering or reduces treatment agent storageability, thus affects treatment agent use.
Complex type organic silicon alkane coupling agent of the present invention shared weight part in epithelium is 20-45 part, if lower than 20 parts, the tack of epithelium and solidity to corrosion can reduce; If more than 45 parts, epithelium ductility deteriorates, easily ftractures in moulding process, causes epithelium punching formation property to reduce.
In addition, the weight ratio of complex type organic silicon alkane coupling agent of the present invention and waterborne cation polyurethane compound resin is between 0.5-1.5, if lower than 0.5, namely urethane compound resin is more, because the chemical bonding ability of urethane compound resin and metal substrate is more weak, the tack of epithelium and solidity to corrosion may be caused to decline.If higher than 1.5, namely organo silane coupling agent is more, and because the fragility of organo silane coupling agent is large, unit elongation is more weak, may cause epithelium ductility deteriorates, easily ftracture in moulding process, thus affects 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 the feature of low surface energy, high lubricity and high surface hardness, epithelial surfaces can be moved to rapidly in treatment agent baking-curing process, thus the lubricant film of one deck hard is formed at epithelial surfaces, not only can improve the wearability of epithelium, epithelial surfaces slipping can also be strengthened, reach the object of strengthening epithelium punching formation property.The polytetrafluoroethylparticle particle diameter (middle several diameter) used is in the scope of 0.3-0.8 micron, if lower than 0.3 micron, polytetrafluoroethylparticle particle is too small, promotes not obvious to the wear resistance of epithelium; If higher than 0.8 micron, polytetrafluoroethylparticle particle is excessive, sole mass is heavier, not easily to epithelial surfaces migration in epithelium solidification process, therefore can not form complete hard lubricant film at epithelial surfaces again, not have the object improving epithelial surfaces slipping.
Surface modification high density polyethylene(HDPE) particle used in the present invention is commercial solid lubricating auxiliary agent, such lubricating auxiliary agent particle surface is grafted with reactive group, and reactive group is one or more in amino, hydroxyl, carboxyl, epoxy group(ing) or carbamate groups.Wherein, high density polyethylene(HDPE) uses the manufacture of Ziegler-Natta polymerization usually, and molecular chain does not have side chain, and molecular chain arrangement is regular, and have higher density, its common density is at 0.940 ~ 0.976g/cm
3in scope, hydroxyl and carboxyl can obtain by being immersed in strong oxidizing solution by high density polyethylene(HDPE) particle; Amino and carbamate groups can pass through quadrol, hexanediamine or urethanum and the grafting of high density polyethylene(HDPE) particle surface obtains; Epoxy group(ing) can be passed through glycidyl methacrylate or glycidyl allyl ether and the grafting of high density polyethylene(HDPE) particle surface and obtain.Above reactive group can react to each other with organo silane coupling agent in treatment solution and form covalent linkage and be connected, not only can strengthen high density polyethylene(HDPE) particle and epithelium cohesive strength, high density polyethylene(HDPE) particle can also be held onto, thus ensure that high density polyethylene(HDPE) particle can be dispersed in epithelium, excellent wear resistance can be provided at the whole thickness direction of epithelium, improve epithelium punch process and wear resistance.Meanwhile, delay corrosive medium along high density polyethylene(HDPE) particle surface to epithelium internal penetration by the chemical bonding formed between high density polyethylene(HDPE) particle and epithelium, reduce adding the corrosion proof negative impact of epithelium of high density polyethylene(HDPE) particle.
Surface modification high density polyethylene(HDPE) particle dia used in the present invention (middle several diameter) is in the scope of 3-5 micron, if lower than 3 microns, high density polyethylene(HDPE) particle does not have the effect strengthening epithelium wearability in epithelium, if higher than 5 microns, solid lubrication aid particle is excessive, and most of particle is exposed to epithelial surfaces, when being subject to punching press friction, macroparticle easily comes off and extracts, and causes the impatient play of the punch process of epithelium to decline.
Composite lubricated ion used in the present invention, the weight ratio of polytetrafluoroethylparticle particle and surface modification high density polyethylene(HDPE) particle is in the scope of 1-3.If lower than 1, the surface modification high density polyethylene(HDPE) particle that is diameter is larger is more, and corrosive medium, easily along major diameter high density polyethylene(HDPE) particle to epithelium internal penetration, may cause the solidity to corrosion of epithelium and surface lubrication to decline; If higher than 3, when namely polytetrafluoroethylparticle particle is more, too much polytetrafluoroethylparticle particle is enriched in epithelial surfaces, and the abrasion resistance of epithelium can be caused inadequate.
Composite lubricated total ion concentration used in the present invention shared weight part in epithelium is 15-25 part.If be less than 15 parts, then not, if be greater than 25 parts, too much solid lubrication aid particle is present in epithelium for epithelial surfaces oilness and abrasion resistance, corrosive medium may be inner along solid lubrication auxiliary agent contacting permeation to epithelium, thus reduce epithelium solidity to corrosion and resistance to acids and bases.
In graphene oxide water solution used in the present invention, the massfraction of graphene oxide is 1-5%, and the graphene oxide used is laminated structure, can be individual layer or multilayer.When graphene oxide is multilayer, lamella quantity is preferably less than 5 layers.By controlling below 5 layers by the graphene oxide number of plies, the flexibility that Graphene keeps excellent can be made, keeping the snappiness of epithelium, and improving the wearability of epithelium.
Wetting ability reactive group is contained on the surface of surface-functionalized graphene oxide water solution, its manufacture method can use current known method, for example, hydroxyl and carboxyl can by ultrasonic disperse process in the strong oxidizing solution (as the vitriol oil/potassium permanganate mixing solutions, the vitriol oil/concentrated nitric acid mixing solutions) that graphene oxide is immersed in 70-80 DEG C 1 hour, then filter and by a large amount of washed with de-ionized water to graphene aqueous solution close to neutral; Amino can pass through quadrol or hexanediamine and surface of graphene oxide grafting and obtain.
Surface-functionalized surface of graphene oxide grafting wetting ability reactive group of the present invention, not only can improve the stably dispersing coefficient of graphene oxide in aqueous surface-treating agent system, prevents it from reuniting or precipitation; Can also strengthen the chemical reaction of organo silane coupling agent or urethane compound resin in graphene oxide and system, thus improve the boundary strength of graphene oxide and other components, oxidation Graphene is to the raising effect of epithelium solidity to corrosion and wearability.The graphene oxide of laminated structure is dispersed in epithelium inside, when corrosive medium is to epithelium internal penetration, graphene oxide lamella can increase the permeation pathway of corrosive medium, plays excellent physical protection effect, thus increases substantially the corrosion resistance nature of epithelium.Meanwhile, be carbon-to-carbon covalent linkage and connect, have excellent mechanical property between graphene oxide lamella atom, the wearing and tearing of object and destruction have good resistant function to external world, thus can play the effect improving epithelium abrasion resistance properties.
In graphene oxide water solution of the present invention or surface-functionalized graphene oxide water solution, graphene oxide shared weight part in epithelium is 0.1-0.5 part.If lower than 0.1 part, when namely graphene oxide is less, graphene oxide to epithelium wearability and corrosion proof raising not obvious; If higher than 0.5 part, when namely graphene oxide is more, the impact of epithelium oxidated Graphene is dimmed, affects outward appearance.Also easily reunite when simultaneous oxidation Graphene is more, reduce epithelial surfaces quality.
Water-soluble fluorine-containing compound of the present invention, the shared weight part in epithelium of the fluorine element in fluorochemicals is 0.5-1.5 part.If when the weight part of fluorine element is lower than 0.5 part, when that is fluorochemicals is less, epithelium solidity to corrosion may decline; If when the weight part of fluorine element is greater than 1.5 parts, when that is fluorochemicals is more, the stability possible deviation of aqueous treatment agent.
Water-soluble P contained compound of the present invention, the shared weight part in epithelium of the phosphoric in P contained compound is 1-2 part.If when the weight part of phosphoric is lower than 1 part, when that is P contained compound is less, do not have additive effect, epithelium solidity to corrosion may decline; If when the weight part of phosphoric is greater than 2 parts, when that is P contained compound is more, epithelium tack may be caused to be deteriorated.
Water-solubility rare-earth salt compounds of the present invention, hydroxyl reaction after rare earth salts compound can be hydrolyzed with organo silane coupling agent in galvanized steel sheet surface zinc coating and treatment solution, form the metallic bond with high bond energy, the rare-earth salts conversion film of the thin compact structure of one deck is formed at Several Thiourea Derivatives on Zinc Plate Surface, shield steel plate physically to contact with the direct of corrosive medium, reduce the possibility that steel plate is corroded, thus expand the ability of erosion under significantly improving the anti-film of steel plate.Rare earth element in water-solubility rare-earth salt compounds shared weight part in epithelium is 0.1-1.5 part.If when the weight part of rare earth element is lower than 0.1 part, when that is water-solubility rare-earth salt compounds is less, do not have additive effect, epithelium solidity to corrosion and tack may decline; If when the weight part of rare earth element is greater than 1.5 parts, that is water-soluble containing rare earth salts compound more time, the stability of aqueous treating fluid can be deteriorated, and may affect the quality of galvanized steel sheet surface process.
The invention provides the method manufacturing and there is the steel plate galvanized of excellent machining property, solidity to corrosion and paintable, steel plate drying temperature is between 80-180 DEG C, if lower than 80 DEG C, then epithelium is crosslinked abundant not, epithelium properties may be caused to decline, if higher than 180 DEG C, then constituent part performance change in treatment solution, may affect film-formation result.
Surface treatment agent of the present invention is coated on galvanized steel sheet surface, its build is between 2-4 micron, during less than 2 microns, because epithelium is thinner, punch process, resistance to acids and bases and wearability may be caused to decline, when leather film thickness is more than 4 microns, the surface treatment cost of unit surface can be increased.
The heat drying mode of the present invention to the aqueous surface-treating agent being coated on galvanized steel sheet surface has no particular limits, and can be Hot-blast Heating, induction heating, Infrared Heating etc.The size, shape etc. of the present invention to steel plate galvanized have no particular limits.
Compared with prior art, beneficial effect of the present invention:
1) the present invention to reduce in waterborne cation polyurethane compound resin as far as possible can with the group of acid-base reaction, as ester group, to make the epithelium of formation, there is excellent resistance to acids and bases.
2) in complex type organic silicon alkane coupling agent of the present invention, double organic alkane coupling agent and single organo silane coupling agent will be carried out the prepolymerization of part, the organic silane compound of synthesis can strengthen the crosslinking degree of epithelium in Z-direction, thus epithelium wearability is improved, and solidity to corrosion strengthens.
3) reactive group in surface modification high density polyethylene(HDPE) particle of the present invention can react to each other with organo silane coupling agent in treatment solution and form covalent linkage and be connected, not only can strengthen high density polyethylene(HDPE) particle and epithelium cohesive strength, high density polyethylene(HDPE) particle can also be held onto, thus ensure that high density polyethylene(HDPE) particle can be dispersed in epithelium, excellent wear resistance can be provided at the whole thickness direction of epithelium, improve epithelium punch process and wear resistance.
4) the present invention is at lamella surface of graphene oxide grafting wetting ability reactive group, improve the stably dispersing coefficient of graphene oxide in aqueous surface-treating agent system, strengthen the chemical reaction of complex type organic silicon alkane coupling agent in graphene oxide and aqueous surface-treating agent system or waterborne cation polyurethane compound resin, thus improving the boundary strength of graphene oxide and other components, oxidation Graphene is to the raising effect of the solidity to corrosion of epithelium and wearability.
5) aqueous surface-treating agent of the present invention is not containing chromium, is environment-friendly type surface treatment agent, and after carrying out surface treatment to steel plate galvanized, steel plate galvanized has excellent surface abrasion resistance, solidity to corrosion and resistance to acids and bases.
Accompanying drawing explanation
The double organic alkane coupling agent structural representation of Fig. 1 for using in embodiment of the present invention 5-8.
Fig. 2 is the dispersion schematic diagram of surface-functionalized graphene oxide used in the present invention in epithelium.
Embodiment
Below in conjunction with specific embodiments the manufacture method of the environmental protection surface treatment agent for steel plate galvanized of the present invention, steel plate galvanized and steel plate galvanized is made further explanation, but this explanation and explanation do not form improper restriction to technical scheme of the present invention.
Embodiment 1-8 and comparative example 1-3
The base material of embodiment 1-8 and comparative example 1-3 all adopts the steel plate galvanized of 0.5mm, and zinc layer weight is 60/60g/m
2in first adopting surface of steel plate, basicity grease-removing agent (pH:9 ~ 10) carries out cleaning showers, then clean with pure water, the alkaline components that removing surface is remaining, the environmental protection surface treatment agent being used for steel plate galvanized is coated in galvanized steel sheet surface, drying is carried out, to form at galvanized steel sheet surface the composite film that thickness is 2-4 micron at 80-180 DEG C.
Table 1 lists the weight part for each component in the environmental protection surface treatment agent of steel plate galvanized in embodiment 1-8 and comparative example 1-3.
Fig. 1 is double organic oxygen alkane (1, the two silica-based ethane of second methoxyl group of 2-) structural representation, can find out, 1, the two silica-based ethane of second methoxyl group of 2-exists 6 can for the alkoxy grp (-OMe group) of reaction, the ability of the chemical bonding between double organic alkane coupling agent and metal substrate or other components can be strengthened, reach strengthening epithelium sticking power and corrosion proof object.
Table 2 lists the drying temperature in embodiment 1-8 and comparative example 1-3 and is coated on the thickness of the composite film that galvanized steel sheet surface is formed.
Fig. 2 is the distribution schematic diagram of surface-functionalized graphene oxide in epithelium, can find out, the graphene oxide of laminated structure is dispersed in epithelium inside, when corrosive medium is to epithelium internal penetration, graphene oxide lamella can increase the permeation pathway of corrosive medium, play excellent physical protection effect, thus increase substantially the corrosion resistance nature of epithelium.
By through in above-described embodiment 1-8 and comparative example 1-3 be used for the environmental protection surface treatment agent coating of steel plate galvanized after steel plate galvanized according to the regulation sampling of following test mode after and test, thus the testing data of obtained its properties of evaluation to be listed in table 3.Wherein, the test evaluating its various performance parameters is as follows:
1) dull and stereotyped solidity to corrosion:
Carry out salt-fog test to flat board, touchstone is ASTMB117, and test period is 120 hours, judgement criteria:
◎: white rust area occupation ratio is less than 5%
Zero: white rust area occupation ratio is greater than 5% and is less than 10%
Δ: white rust area occupation ratio is greater than 10% and is less than 50%
×: white rust area occupation ratio is greater than 50%
2) shaping rear solidity to corrosion:
Use Sven-Gan Eriksson cupping instrument to carry out 8mm cupping, carry out salt-fog test to cupping position, touchstone is ASTMB117, and test period is 72 hours, judgement criteria:
◎: cupping position white rust area occupation ratio is less than 5%
Zero: cupping position white rust area occupation ratio is greater than 5% and is less than 10%
Δ: cupping position white rust area occupation ratio is greater than 10% and is less than 50%
×: cupping position white rust area occupation ratio is greater than 50%
3) solidity to corrosion after alkali cleaning:
Use middle basicity grease-removing agent (pH:9-11) to clean, at 50 DEG C of temperature, spray 3 minutes, carry out salt-fog test to model after cleaning, touchstone is ASTMB117, and test period is 240 hours, judgement criteria:
◎: white rust area occupation ratio is less than 5%
Zero: white rust area occupation ratio is greater than 5% and is less than 10%
Δ: white rust area occupation ratio is greater than 10% and is less than 50%
×: white rust area occupation ratio is greater than 50%
4) punching formation property:
Use the sample preparation of bead method.Experiment condition: fixing pearl overdraft 3KN, pressure head diameter 9.6mm, drawing speed 200mm/min, judgement criteria:
◎: outward appearance is unchanged
Zero: a small amount of stain of outward appearance
Δ: the more obvious blackstreak of outward appearance
×: outward appearance is turned black comprehensively
5) wearability:
Adopt rubber abrasion method, load 500g, stroke distances 20mm, speed 300mm/min, repeated wear 50 times, judgement criteria:
◎: epithelium is unchanged
Zero: epithelium abrades on a small quantity
Δ: epithelium many places abrade
×: epithelium comes off completely
6) alkali resistance:
Be soak 10min in the normal temperature NaOH solution of 1% in concentration, the change of visual observation appearance after rinsing with water, judgement criteria:
◎: outward appearance is unchanged
Zero: outward appearance slight trace
Δ: the obvious albefaction of outward appearance and epithelium are partly dissolved
×: epithelium dissolves completely
7) acid resistance:
Be soak 10min in the normal temperature HCl solution of 1% in concentration, the change of visual observation appearance after rinsing with water, judgement criteria:
◎: outward appearance is unchanged
Zero: outward appearance slight trace
Δ: the obvious albefaction of outward appearance and epithelium are partly dissolved
×: epithelium dissolves completely
8) paintable:
After carrying out application through surface-treated steel plate galvanized according to following condition, carry out painting adhesion test, test conditions:
1. alkyd system whitewash (Shanghai Chenhua Paint MFG. Co.'s product, the trade mark: A-09), the coating of 22# rod, baking condition: 140 DEG C are toasted 40 minutes;
2. epoxide powder coating (Akzo Nobel N.V.'s product, the trade mark: EA05BH), dust layer thickness 70-80 micron, baking condition: 200 DEG C are toasted 10 minutes;
After above-mentioned two coating of coating, adopt cutter to draw 100 little lattice in film coated surface, size is 1mm
2, the degree of depth should draw paint film layer to reach surface of steel plate.After adopting cellotape to peel off, observe the residual lattice number of paint film, residual lattice number is more, illustrates that steel plate can be more excellent for the paintable of alkyd system whitewash or epoxide powder coating.
Table 3 list by embodiment 1-8 and comparative example 1-3 through environmental protection surface treatment agent apply after steel plate galvanized sampling after tested after various performance parameters.
As can be seen from Table 3, the steel plate galvanized after the coating of environmental protection surface treatment agent in employing embodiment 1-8 is after above-mentioned every test, its evaluation result is " ◎ " and "○", and its paintable is also better, illustrate that the steel plate galvanized being coated with the environment-friendly water-based surface treatment agent of the present invention all has the excellent or good over-all properties such as erosion resistance (after dull and stereotyped, shaping and after alkali cleaning), processibility, wearability, resistance to acids and bases and paintable.
Associative list 1 and table 3 can be known, compared to embodiment 1-8, owing to there is no function of surface functionalized graphene in the environmental protection surface treatment agent of comparative example 1, and the weight part of urethane compound resin is in lower limit, therefore, the solidity to corrosion of steel plate galvanized, punch process and wearability after being applied by this environmental protection surface treatment agent are all poor.In addition, weight part due to the environmental protection surface treatment agent solid lubrication particle of comparative example 2 is less and the weight part of P contained compound is in the upper limit, so the solidity to corrosion of epithelium of the steel plate galvanized after being applied by this environmental protection surface treatment agent, processibility and wearability are poor.In addition, the weight part of the metal-rare-earth salt compound in the environmental protection surface treatment agent of comparative example 3 is less, and thus, solidity to corrosion and the alkali resistance of the steel plate galvanized after the coating of this environmental protection surface treatment agent are poor.
Visible, steel plate galvanized of the present invention has excellent surface wearability, solidity to corrosion and resistance to acids and bases, meets that multiple field user damages the environmental protection of steel plate galvanized, surface abrasion resistance, the requirement of punch process and defatting-bonderizing.
It should be noted that above enumerate be only specific embodiments of the invention, obviously the invention is not restricted to above embodiment, have many similar changes thereupon.If all distortion that those skilled in the art directly derives from content disclosed by the invention or associates, protection scope of the present invention all should be belonged to.
Metatitanic acid; F1 is ortho-phosphoric acid, and F2 is ammonium phosphate; G1 is ceric ammonium nitrate, and G2 is lanthanum nitrate, and G3 is potassium chlorate fluozirconate.
Table 2
| Sequence 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 (24)
1. have the steel plate galvanized of excellent surface wearability, solidity to corrosion and resistance to acids and bases, its surface coverage Organic-inorganic composite epithelium, this epithelium contains:
A) waterborne cation polyurethane compound resin, the weight part in epithelium is 30-50 part; Described waterborne cation polyurethane compound resin is formed by one or more and the base polyurethane prepolymer for use as copolymerization be selected from PTMG, polyacrylic ester or poly-perfluoroalkyl acrylate, and relative molecular weight is 80000-150000;
B) complex type organic silicon alkane coupling agent, the weight part in epithelium is 20-45 part; Described complex type organic silicon alkane coupling agent is the mixture of at least one double organic alkane coupling agent and at least one list organo silane coupling agent; Described double organic alkane coupling agent is containing bridging structure, and the weight ratio of described double organic alkane coupling agent and single organo silane coupling agent is 0.3-2;
C) composite lubricated particle, the weight part in epithelium is 15-25 part; Described composite lubricated particle comprises polytetrafluoroethylparticle particle and surface modification high density polyethylene(HDPE) particle;
D) graphene oxide water solution, wherein the weight part of graphene oxide in epithelium is 0.1-0.5 part; In described graphene oxide water solution, the massfraction of graphene oxide is 1-5%;
E) water-soluble fluorine-containing compound, wherein the weight part of fluorine element in epithelium is 0.5-1.5 part;
F) water-soluble P contained compound, wherein the weight part of phosphoric in epithelium is 1-2 part;
G) water-solubility rare-earth salt compounds, the weight part of its rare earth elements in epithelium is 0.1-1.5 part.
2. the steel plate galvanized with excellent surface wearability, solidity to corrosion and resistance to acids and bases according to claim 1, is characterized in that, described Organic-inorganic composite protective membrane is single layer structure, and its film thickness range is 2-4 micron.
3. the steel plate galvanized with excellent surface wearability, solidity to corrosion and resistance to acids and bases according to claim 1, is characterized in that, the described weight part of waterborne cation polyurethane compound resin (A) in epithelium is 35-45 part.
4. the steel plate galvanized with excellent surface wearability, solidity to corrosion and resistance to acids and bases according to claim 1, it is characterized in that, when preparing waterborne cation polyurethane compound resin (A), described base polyurethane prepolymer for use as obtains by not reacting containing the polyol compounds of ester group and aliphatic isocyanates or aromatic isocyanate compound.
5. the steel plate galvanized with excellent surface wearability, solidity to corrosion and resistance to acids and bases according to claim 1, it is characterized in that, in described complex type organic silicon alkane coupling agent (B), the bridging structure of described double organic alkane coupling agent is made up of 2-4 methylene radical, amino or sulfydryl.
6. the steel plate galvanized with excellent surface wearability, solidity to corrosion and resistance to acids and bases according to claim 1, it is characterized in that, in described complex type organic silicon alkane coupling agent (B), at least there is reactive group containing one in the molecule of described single organo silane coupling agent, described in there is reactive group for amino, epoxy group(ing) or vinyl.
7. the steel plate galvanized with excellent surface wearability, solidity to corrosion and resistance to acids and bases according to claim 1, it is characterized in that, described complex type organic silicon alkane coupling agent (B) and the weight ratio of waterborne cation polyurethane compound resin (A) are 0.5-1.5.
8. the steel plate galvanized with excellent surface wearability, solidity to corrosion and resistance to acids and bases according to claim 1, it is characterized in that, in described composite lubricated particle (C), the weight ratio of polytetrafluoroethylparticle particle and surface modification high density polyethylene(HDPE) particle is 1-3; Described polytetrafluoroethylparticle particle diameter (middle several diameter) is 0.3-0.8 micron, and described surface modification high density polyethylene(HDPE) particle dia (middle several diameter) is 3-5 micron.
9. the steel plate galvanized with excellent surface wearability, solidity to corrosion and resistance to acids and bases according to claim 8, it is characterized in that, described surface modification high density polyethylene(HDPE) particle surface is grafted with reactive group, and described reactive group is one or more in amino, hydroxyl, carboxyl, epoxy group(ing) or carbamate groups.
10. the steel plate galvanized with excellent surface wearability, solidity to corrosion and resistance to acids and bases according to claim 1, it is characterized in that, described graphene oxide water solution (D) is surface-functionalized graphene oxide water solution, described surface-functionalized graphene oxide refers to and is grafted with wetting ability reactive group in surface of graphene oxide, and described wetting ability reactive group is one or more in amino, hydroxyl and carboxyl.
11. steel plate galvanizeds with excellent surface wearability, solidity to corrosion and resistance to acids and bases according to claim 1 or 10, it is characterized in that, in described graphene oxide water solution (D), described graphene oxide is individual layer or multilayer, when graphene oxide is multilayer, lamella quantity is less than 5 layers.
12. steel plate galvanizeds with excellent surface wearability, solidity to corrosion and resistance to acids and bases according to claim 1, it is characterized in that, described water-soluble fluorine-containing compound (E) is fluorine-containing metallic salt or fluorine-containing acids, one or more in preferred fluorinated sodium, ammonium titanium fluoride, Sodium Silicofluoride, hexafluorotitanic acid and silicofluoric acid.
13. steel plate galvanizeds with excellent surface wearability, solidity to corrosion and resistance to acids and bases according to claim 1, it is characterized in that, described water-soluble P contained compound (F) is phosphoric acid salt or phosphorous acids, one or more in preferred ortho-phosphoric acid, tetra-sodium, tripolyphosphate, trimerization metaphosphoric acid, ammonium phosphate, aluminium triphosphate and ammonium polyphosphate.
14. steel plate galvanizeds with excellent surface wearability, solidity to corrosion and resistance to acids and bases according to claim 1, it is characterized in that, described water-solubility rare-earth salt compounds (G) is cerium salt, at least one in La-salt and rare earth zirconates; Cerium salt be preferably in cerous nitrate, cerous sulfate, fluorine-containing cerium salt, cerium ammonium compound salt one or more; La-salt be preferably in Lanthanum trichloride, lanthanum sulfat and lanthanum nitrate one or more; Rare earth zirconates be preferably in potassium chlorate fluozirconate, zirconium nitrate and zirconium sulfate one or more.
15. steel plate galvanized use surface treatment agents with excellent surface wearability, solidity to corrosion and resistance to acids and bases as described in any one of claim 1-14, in its aqueous solution, total solids part contains following composition:
A) waterborne cation polyurethane compound resin, the weight part in epithelium is 30-50 part; Described waterborne cation polyurethane compound resin is formed by one or more in PTMG, polyacrylic ester or poly-perfluoroalkyl acrylate and base polyurethane prepolymer for use as copolymerization, and relative molecular weight is 80000-150000;
B) complex type organic silicon alkane coupling agent, the weight part in epithelium is 20-45 part; The coupling of described complex type organic silicon alkane is the mixture of at least one double organic alkane coupling agent and at least one list organo silane coupling agent; Described double organic alkane coupling agent is containing bridging structure, and the weight ratio of described double organic alkane coupling agent and single organo silane coupling agent is 0.3-2;
C) composite lubricated particle, the weight part in epithelium is 15-25 part; Described composite lubricated particle comprises polytetrafluoroethylparticle particle and surface modification high density polyethylene(HDPE) particle;
D) graphene oxide water solution, wherein the weight part of graphene oxide in epithelium is 0.1-0.5 part; In described graphene oxide water solution, the massfraction of graphene oxide is 1-5%;
E) water-soluble fluorine-containing compound, wherein the weight part of fluorine element in epithelium is 0.5-1.5 part;
F) water-soluble P contained compound, wherein the weight part of phosphoric in epithelium is 1-2 part;
G) water-solubility rare-earth salt compounds, the weight part of its rare earth elements in epithelium is 0.1-1.5 part.
The 16. steel plate galvanized use surface treatment agents as claimed in claim 15 with excellent surface wearability, solidity to corrosion and resistance to acids and bases, it is characterized in that, the described weight part of waterborne cation polyurethane compound resin (A) in epithelium is 35-45 part.
The 17. steel plate galvanized use surface treatment agents as claimed in claim 15 with excellent surface wearability, solidity to corrosion and resistance to acids and bases, it is characterized in that, when preparing waterborne cation polyurethane compound resin (A), described base polyurethane prepolymer for use as obtains by not reacting containing the polyol compounds of ester group and aliphatic isocyanates or aromatic isocyanate compound.
The 18. steel plate galvanized use surface treatment agents with excellent surface wearability, solidity to corrosion and resistance to acids and bases stated as claim 15, it is characterized in that, in described complex type organic silicon alkane coupling agent (B), the bridging structure of described double organic alkane coupling agent is made up of 2-4 methylene radical, amino or sulfydryl; At least there is reactive group containing one in the molecule of described single organo silane coupling agent, described in there is reactive group for amino, epoxy group(ing) or vinyl.
The 19. steel plate galvanized use surface treatment agents as claimed in claim 15 with excellent surface wearability, solidity to corrosion and resistance to acids and bases, it is characterized in that, described complex type organic silicon alkane coupling agent (B) and the weight ratio of waterborne cation polyurethane compound resin (A) are 0.5-1.5.
The 20. steel plate galvanized use surface treatment agents as claimed in claim 15 with excellent surface wearability, solidity to corrosion and resistance to acids and bases, it is characterized in that, in described composite lubricated particle (C), the weight ratio of polytetrafluoroethylparticle particle and surface modification high density polyethylene(HDPE) particle is 1-3; Described polytetrafluoroethylparticle particle diameter (middle several diameter) is 0.3-0.8 micron, and described surface modification high density polyethylene(HDPE) particle dia (middle several diameter) is 3-5 micron.
The 21. steel plate galvanized use surface treatment agents as claimed in claim 20 with excellent surface wearability, solidity to corrosion and resistance to acids and bases, it is characterized in that, described surface modification high density polyethylene(HDPE) particle surface is grafted with reactive group, and described reactive group is one or more in amino, hydroxyl, carboxyl, epoxy group(ing) or carbamate groups.
The 22. steel plate galvanized use surface treatment agents as claimed in claim 15 with excellent surface wearability, solidity to corrosion and resistance to acids and bases, it is characterized in that, described graphene oxide water solution (D) is surface-functionalized graphene oxide water solution, described surface-functionalized graphene oxide refers to and is grafted with wetting ability reactive group in surface of graphene oxide, and described wetting ability reactive group is one or more in amino, hydroxyl and carboxyl.
23. steel plate galvanized use surface treatment agents with excellent surface wearability, solidity to corrosion and resistance to acids and bases as described in any one of claim 15-22, it is characterized in that, described water-soluble fluorine-containing compound (E) is fluorine-containing metallic salt or fluorine-containing acids, described water-soluble P contained compound (F) is phosphoric acid salt or phosphorous acids, and described water-solubility rare-earth salt compounds (G) is cerium salt, at least one in La-salt and rare earth zirconates.
24. as arbitrary in claim 1-14 as described in a kind of preparation method with the steel plate galvanized of excellent surface wearability, solidity to corrosion and resistance to acids and bases, aqueous surface-treating agent described in any one of claim 15-23 is coated to surface by a roller coat, and drying is carried out between 80-180 DEG C, make build at 2-4 micron.
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