CN1290940C - Anti-corrosion paint for metal with improved corrosion resistance - Google Patents
Anti-corrosion paint for metal with improved corrosion resistance Download PDFInfo
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- CN1290940C CN1290940C CN 200510069412 CN200510069412A CN1290940C CN 1290940 C CN1290940 C CN 1290940C CN 200510069412 CN200510069412 CN 200510069412 CN 200510069412 A CN200510069412 A CN 200510069412A CN 1290940 C CN1290940 C CN 1290940C
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Abstract
The present invention relates to corrosion resistant paint for metal, and the paint has with improved corrosion resistance. The paint is prepared from the following components: 23 to 32 wt% of metal powder, 1 to 5 wt% of film-forming auxiliary agent, 4 to 9 wt% of cosolvent, 0.8 to 2.2 wt% of surfactant, 3.2 to 10.2 wt% of coupling agent, 0.1 to 1.2 wt% of preservative agent, 0.5 to 15 wt% of heat convertible resin, 0.08 to 0.3 wt% of thickening agent and deionized water as the rest, wherein zinc powder and aluminium powder in the metal powder are both in a flake state, the flake diameter is smaller than 20 mum, and the weight ratio of the zinc powder to the aluminium powder is from 4:1 to 12:1; in addition, the titanium powder is granular whose diameter is smaller than 2 mum, and the titanium powder accounts for 1 to 6.5 wt% of the total amount of the metal powder. In addition, the paint can also comprise 0.1 to 2 wt% of thiocarbonyl compound. The paint of the present invention is zinc powder paint which has the advantages of high corrosion resistance and favorable environmental protection property.
Description
Technical field
The present invention relates to a kind of protective system, and this protective system has splendid environment friendly.
Background technology
Because the electropotential of zinc is more negative, when its during with the metallic contact of current potential calibration, self can at first take place to corrode and the metal of protection potential calibration.Therefore, zinc powder is used in all kinds of coated layers by people as a kind of efficient corrosion resisting filler.
As CN1357581A disclosed " anticorrosion and antistatic method of oil filler pipe assembly and matched coating thereof ", this patent with Resins, epoxy as base-material, zinc powder as main stuffing, non-ketoimine as linking agent, and interpolation water-retaining agent, coatings formulated has good solidity to corrosion and stability, but having only thickness to reach, this patent coating just has excellent solidity to corrosion about 50 μ m, and this patent coating is difficult to the preparation shallow layer as less than 5 μ m, and this makes its application in some fields such as Investment in fastener industry be restricted.This patent coating belongs to solvent based coating in addition, can pollute environment.
As CN1422909A disclosed " manufacture method of water-based inorganic two-component zinc-rich paint and this coating ", this coating with silicon sol, lithium silicate as cakingagent, coating according to this patent manufacturing has excellent antiseptic property, but the coating coating thickness generally all surpasses 50 μ m, this makes its application in some fields such as Investment in fastener industry be restricted, after two components are mixed in this patent simultaneously, in 8 hours even shorter time,, coating just may not lose efficacy if carrying out application.
As CN1323860A disclosed " non-electrolytic metal corrosion preventing paint "; this coating is with flake zinc powder and aluminium powder; organic reducing agent, tensio-active agent and chromic salts preparation coating; though this coating has good anti-corrosion capability and excellent stability; but, be unfavorable for environment protection because sexavalent chrome belongs to the heavily contaminated material.
Summary of the invention
In order to solve in the prior art, the corrosion resisting property of coating compound and environment friendly problem the purpose of this invention is to provide the metal anti-corrosive paint that a kind of corrosion resisting property has improved, and are the zinc powder coating with high anti-corrosion and excellent environmental protection property.
To achieve these goals, the present invention takes following technical proposals:
The metal anti-corrosive paint that a kind of corrosion resisting property has improved, this coating is made up of the component of following content:
Metal-powder is 23-32 weight %, described metal-powder is zinc powder, aluminium powder and titanium valve, wherein, zinc powder and aluminium powder are sheet, the sheet footpath is less than 20 μ m, and zinc powder and aluminium powder part by weight are 4: 1~12: 1, and titanium valve is granular, particle diameter is less than 2 μ m, and titanium valve accounts for the 1-6.5 weight % of metal-powder total amount;
Film coalescence aid is 1-5%;
Solubility promoter is 4-9 weight %;
Tensio-active agent is 0.8-2.2 weight %;
Coupling agent is 3.2-10.2 weight %;
Sanitas is 0.2-1.2 weight %;
Thermosetting resin is 0.5-15 weight %;
Thickening material is 0.08-0.3 weight %;
Deionized water is a surplus.
The metal anti-corrosive paint that another kind of corrosion resisting property has improved, this coating is made up of the component of following content:
Metal-powder is 23-32 weight %, described metal-powder is zinc powder, aluminium powder and titanium valve, wherein, zinc powder and aluminium powder are sheet, the sheet footpath is less than 20 μ m, and zinc powder and aluminium powder part by weight are 4: 1~12: 1, and titanium valve is granular, particle diameter is less than 2 μ m, and titanium valve accounts for the 1-6.5 weight % of metal-powder total amount;
Film coalescence aid is 1-5%;
Solubility promoter is 4-9 weight %;
Tensio-active agent is 0.8-2.2 weight %;
Coupling agent is 3.2-10.2 weight %;
Sanitas is 0.2-1.2 weight %;
Thiocarbonyl compound is 0.1-2 weight %, and wherein, thiocarbonyl compound is one or more in thiocarbamide, alkyl thiourea and the thioacetamide;
Thermosetting resin is 0.5-15 weight %;
Thickening material is 0.08-0.3 weight %;
Deionized water is a surplus.
The metal anti-corrosive paint difference that above-mentioned two kinds of corrosion resisting properties have improved and the distinguishing characteristics of prior art are: metal anti-corrosive paint of the present invention has added purification ultrafine titanium powder, and interpolation flake zinc powder and aluminium powder can strengthen the corrosion resistance coating energy in coating.
The metal anti-corrosive paint that the metal anti-corrosive paint that second kind of corrosion resisting property improved and first kind of corrosion resisting property have improved is compared, the metal anti-corrosive paint that second kind of corrosion resisting property improved has increased thiocarbonyl compound, can further strengthen the corrosion resisting property of coating.
Component in metal anti-corrosive paint of the present invention specifies as follows:
Described metal-powder is zinc powder, aluminium powder and titanium valve; wherein zinc powder and aluminium powder are sheet (the sheet footpath is less than 20 μ m); zinc powder and aluminium powder part by weight can for 4: 1 until 12: 1; wherein titanium valve is granular (particle diameter is less than 2 μ m); titanium valve accounts for the 1%-6.5% of metal-powder gross weight; the effect of metal-powder is to be used for improving corrosion resistance coating by galvanic protection effect and physical shielding, and its total amount proportion in coating is 23-32 weight %.
Described film coalescence aid can use known film coalescence aid, preferred film coalescence aid is glycol ether or glycol ether ester, propylene glycol or propylene glycol ether-ether class, No. 200 solvent oils or 2,2,4-trimethylammonium-1, in the 3-pentanediol mono isobutyrate one or more, its total amount proportion in coating is 1-5 weight %.
Described solubility promoter can use known solubility promoter, preferred solubility promoter is one or more in alcohols such as Virahol, the trimethyl carbinol, ethylene glycol and ethers thereof or propylene glycol and the ethers thereof, solubility promoter is to improve film forming properties when coating curing, and its total amount proportion in coating is 4-9 weight %.
Described tensio-active agent can use known tensio-active agent, preferred surfactants is one or more in fatty acid Soxylat A 25-7, alkyl phenol ethylene oxide condensate and the polyoxyethylene nonylphenol ether, Action of Surfactant is to improve the dispersive ability of metal-powder in solvent, and its total amount proportion in coating is 0.8-2.2 weight %.
Described coupling agent can use known coupling agent, preferred coupling agent is the phthalate coupling agent, β-alcoxyl second carboxyl two (dioctyl pyrophosphate) titanium as chelating 100 types, trolamine phthalate etc., it also can be silane coupling agent, as γ-glycidyl ether oxygen propyl trimethoxy silicane, N-β-(aminoethyl)-γ-An Bingjisanjiayangjiguiwan etc., action of coupling agents is to improve the dispersive ability of metal-powder in solvent and the sticking power that strengthens metal-powder and base material, and proportion is 3.2-10.2 weight % in coating.
Described sanitas can use known sanitas, preferred sanitas is inorganic salts such as ammonium phosphate, in the basic metal of phytic acid root, nitrate radical, carbonate or inferior sulfate radical or the alkaline earth salt one or more, the effect of sanitas is by strengthening between the zinc powder and the sequestering action of zinc powder and matrix, thereby improve adhesive force of coatings and corrosion resisting property, its total amount proportion in coating is 0.2-1.2 weight %.
Described thiocarbonyl compound is one or more in thiocarbamide, alkyl thiourea and the thioacetamide, and the effect of thiocarbonyl compound is to the metal-powder surface passivation, strengthens the corrosion resistance coating energy, and its total amount proportion in coating is 0.1-2 weight %.
Described thermosetting resin can use known thermosetting resin, preferred thermosetting resin is one or more in water-soluble polypropylene acid resin, water-soluble organic silicon resin and the water-soluble epoxy resin, the effect of thermosetting resin is to strengthen the dispersiveness of metal-powder in solvent also also to improve between the zinc powder and the sticking power between zinc powder and the base material, and its total amount proportion in coating is 0.5-15 weight %.
Described thickening material can use known thickening material, preferred thickening is a cellulose family, as Natvosol, methylhydroxypropylcellulose, it also can be the thickening material of other type, the effect of thickening material is to regulate the viscosity of coating to be fit to application, and proportion is 0.08-0.3 weight % in coating.
The coating remaining part is a deionized water.
For prepare a kind of improved stability of the present invention protective system, each component in the protective system of the present invention can be divided into two kinds of components of A, B, coating promptly of the present invention is formulated by following A, two kinds of components of B.Component A comprises metal-powder, film coalescence aid, solubility promoter, tensio-active agent, contains the sulfo-carbonyl compound metal anti-corrosive paint of second kind of improved stability (), coupling agent, sanitas.The B component comprises deionized water, thermosetting resin, thickening material.
Manufacture craft of the present invention is: at first with film coalescence aid, solubility promoter, tensio-active agent, thiocarbonyl compound the metal anti-corrosive paint of second kind of improved stability (), coupling agent, sanitas are mixed in proportion, after agitation as appropriate mixes each component, while stirring metal-powder is added in the said mixture, continue to be stirred to each component and be uniformly dispersed fully, promptly make component A.Getting thickening material and thermosetting resin in proportion adds in the deionized water, stirring mixes it, for making mixture reach uniformity rapidly, deionized water can be heated to about 50 ℃ and then interpolation thickening material and thermosetting resin, also can be by adding acidulous material, as boric acid, the pH value of regulating deionized water is between the 6-8, more than promptly make B component.During use, under stirring state, slowly add B component to component A, stir and directly to be coated to the metallic surface later in 10 hours, coating can be directly in baking curing in about 30 minutes about 300 ℃, but recommend at first drying by the fire about 10 minutes about 180 ℃ for obtaining better coating performance, and then baking was solidified in 15 minutes about 300 ℃, more than operation can form the high anti-corrosion corrosion protection coating in the metallic surface.
Advantage of the present invention:
1, the present invention has added thiocarbonyl compound, and sulfide has very strong oxidisability, when it is adsorbed on the metallic surface, can play passivation to the metallic surface.Partial reaction can take place and generate stable ZnS film on the zinc powder surface in sulfide and zinc, and this tunic can obviously prolong coating and go out the white rust time, and then strengthens the corrosion resisting property of coating.
2, the present invention has added purification ultrafine titanium powder, and interpolation flake zinc powder and aluminium powder can strengthen the corrosion resistance coating energy in coating, are well known.Yet Zhi Bei coating can have been observed a lot of spaces under high power digital display micro mirror like this, and these spaces have reduced the perviousness of coating erosion resistance medium.Titanium is very easily oxidation in air, therefore is difficult to its simple substance is prepared into the ultra-fine grain diameter powder.The inventor finds that having technology at present can prepare ultra-fine grain diameter metal titanium powder, and this superfine metal titanium valve is added in the coating, can effectively reduce voidage, thereby strengthen the corrosion resisting property of coating.When coat-thickness was not less than 25 μ m, its anti-neutral salt spray time was above 500 hours.
3, the present invention has selected a kind of thermosetting resin for use, has stable memory property at normal temperatures, not can with other composition generation untoward reaction in the component, this thermosetting resin obviously improves the storage stability of coating, can be with the zinc-rich paint of routine by extending to 48 hours even longer about 8 hours work-ing life.
4, the coating that forms in the metallic surface of the coating of manufacturing of the present invention is the thinnest can be 5 μ m, even it is lower, and corrosion resistance nature with excellence, such as thickness only is the coating of 5 μ m, anti-neutral salt spray test can surpass 240 hours, therefore can be applied in fastening piece, brake flange and all relate on the part of requirement for anticorrosion.
Embodiment
Embodiment one:
At first accurately weighing 1.43 gram ethylene glycol ether acetates, 4.5 gram Virahols and 1.8 gram alkyl phenol ethylene oxide condensates mix, under stirring state, slowly add 1.8 gram alkyl thioureas, 10.1 gram β-alcoxyl second carboxyl two (dioctyl pyrophosphate) titaniums successively, make liquid form mixt after fully stirring, again 18.62 gram zinc flakes, 4.2 gram flake aluminums, 1.48 gram particle shape titanium valves and 1.16 gram sodium phytates are added in the said mixture, continue to stir more than 2 hours to each component and be uniformly dispersed fully, promptly make component A.Claim the deionized water of 54.03 grams, be heated to 50 ℃, add the Natvosol of 0.28 gram and the water-soluble epoxy resin of 0.6 gram successively, fully stir, promptly make B component until mixing.
Under stirring state, slowly add B component to component A, stir and made slurries in 10 hours later on, apply operation, coating is directly in baking curing in about 30 minutes about 300 ℃, but recommend at first drying by the fire about 10 minutes about 180 ℃ for obtaining better coating performance, and then baking was solidified in 15 minutes about 300 ℃, more than operation can form the high anti-corrosion corrosion protection coating in the metallic surface.This corrosion protection coating is surveyed sticking power with the adhesive tape method can reach 5 grades, and during coat-thickness 5 μ m, neutral salt spray test the red rust time occurred above 240 hours.
Embodiment two:
At first accurately weighing 1.2 restrains 2,2,4-trimethylammonium-1, the 3-pentanediol mono isobutyrate, 0.8 restrain solvent oil No. 200,6.3 gram ethylene glycol and 1.47 gram fatty acid Soxylat A 25-7s mix, under stirring state, slowly add 0.9 gram thioacetamide successively, 7.26 gram N-β-(aminoethyl)-γ-An Bingjisanjiayangjiguiwan, make liquid form mixt after fully stirring, again with 25.8 gram zinc flakes, 3.2 gram flake aluminum, 0.36 gram particle shape titanium valve and 0.8 gram ammonium phosphate add in the said mixture, continue to stir more than 2 hours to each component and be uniformly dispersed fully, promptly make component A.The deionized water that claims 49.63 grams, the boric acid that adds 0.2 gram stirs directly dissolving fully, adjusts pH value and is about 6.8, adds the methylhydroxypropylcellulose of 0.08 gram and the water-soluble organic silicon resin of 2.2 grams then successively, fully stir, promptly make B component until mixing.During use, under stirring state, slowly add B component to component A, stir and to use for applying later in 10 hours.
The above-mentioned coating that mixes after 48 hours, is applied preparation coating by embodiment one described method 25 ℃ of sealing and standing.The gained coating is surveyed sticking power with the adhesive tape method still can reach 4.5 grades, and during coat-thickness 25 μ m, neutral salt spray test the red rust time occurred above 500 hours.
Embodiment three:
At first accurately weighing 4.78 gram ethylene glycol ethyl ethers, 4.7 gram Virahols, 4 gram propylene glycol and 1.1 gram polyoxyethylene nonylphenol ethers mix, under stirring state, slowly add 4.1 gram trolamine phthalates, make liquid form mixt after fully stirring, again 28.3 gram zinc flakes, 2.6 gram flake aluminums, 0.8 gram particle shape titanium valve and 0.4 gram lime carbonate are added in the said mixture, continue to stir more than 2 hours to each component and be uniformly dispersed fully, promptly make component A.Claim the deionized water of 44.29 grams and the boric acid of 0.45 gram, be heated to 50 ℃ it is dissolved fully, add the water soluble acrylic resin of the Natvosol and 4.8 grams of 0.13 gram successively, fully stir, promptly make B component until mixing.During use, under stirring state, slowly add B component to component A, stir and to use for applying later in 10 hours.
Press the described method of embodiment one and apply the preparation coating, the gained coating can reach 4.5 grades with adhesive tape method survey sticking power, and during coat-thickness 10 μ m, neutral salt spray test white rust occurred after 24 hours, does not occur red rust in 360 hours later on yet.
Embodiment four:
Press embodiment three method formulation components A and B component, different is when formulation components A, added 0.2 gram thiocarbamide before adding metal-powder, and deionized water is 44.09 grams, and other all are same as embodiment three.
Press embodiment one described method and apply the preparation coating, this corrosion protection coating is surveyed sticking power with the adhesive tape method can reach 4.5 grades, and during coat-thickness 10 μ m, a small amount of white rust just appears in neutral salt spray test after 72 hours, does not occur red rust after 360 hours yet.
Claims (2)
1, the metal anti-corrosive paint that improved of a kind of corrosion resisting property, it is characterized in that: this coating is made up of the component of following content:
Metal-powder is 23-32 weight %, described metal-powder is zinc powder, aluminium powder and titanium valve, wherein, zinc powder and aluminium powder are sheet, the sheet footpath is less than 20 μ m, and zinc powder and aluminium powder part by weight are 4: 1~12: 1, and titanium valve is granular, particle diameter is less than 2 μ m, and titanium valve accounts for the 1-6.5 weight % of metal-powder total amount;
Film coalescence aid is 1-5%;
Solubility promoter is 4-9 weight %;
Tensio-active agent is 0.8-2.2 weight %;
Coupling agent is 3.2-10.2 weight %;
Sanitas is 0.2-1.2 weight %;
Thermosetting resin is 0.5-15 weight %;
Thickening material is 0.08-0.3 weight %;
Deionized water is a surplus.
2, the metal anti-corrosive paint that improved of a kind of corrosion resisting property, it is characterized in that: this coating is made up of the component of following content:
Metal-powder is 23-32 weight %, described metal-powder is zinc powder, aluminium powder and titanium valve, wherein, zinc powder and aluminium powder are sheet, the sheet footpath is less than 20 μ m, and zinc powder and aluminium powder part by weight are 4: 1~12: 1, and titanium valve is granular, particle diameter is less than 2 μ m, and titanium valve accounts for the 1-6.5 weight % of metal-powder total amount;
Film coalescence aid is 1-5%;
Solubility promoter is 4-9 weight %;
Tensio-active agent is 0.8-2.2 weight %;
Coupling agent is 3.2-10.2 weight %;
Sanitas is 0.2-1.2 weight %;
Thiocarbonyl compound is 0.1-2 weight %, and wherein, thiocarbonyl compound is one or more in thiocarbamide, alkyl thiourea and the thioacetamide;
Thermosetting resin is 0.5-15 weight %;
Thickening material is 0.08-0.3 weight %;
Deionized water is a surplus.
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KR101842555B1 (en) * | 2015-12-09 | 2018-03-27 | 주식회사 포스코 | Composition for surface-treating a plated steel sheet, surface-treated steel sheet using the same composition, and the method for surface-treatenting using the same composition |
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