CN101033363A - Environment-friendly type galvanizing metal surface treating agent - Google Patents

Environment-friendly type galvanizing metal surface treating agent Download PDF

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CN101033363A
CN101033363A CN 200710010966 CN200710010966A CN101033363A CN 101033363 A CN101033363 A CN 101033363A CN 200710010966 CN200710010966 CN 200710010966 CN 200710010966 A CN200710010966 A CN 200710010966A CN 101033363 A CN101033363 A CN 101033363A
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metal surface
agent
chromium
surface treatment
weight
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CN100584908C (en
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徐同宽
曲丰作
崔励
于长顺
谭凤芝
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Dalian Polytechnic University
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Dalian Polytechnic University
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Abstract

The invention provides a kind of metal surface disposal which formes an environment friendly waterbase film to inhibit corrosion of the metal surface, and the disposal particularly brings excellent anti-corrosion properties with the galvanized metal products. The metal surface disposal basically contains following components which take alcohol and water as the solvent: A. silicates, polymerization silicates, fluoride silicates, B. silica (aqueous dispersion of nano) and / or SinOmXR1R2R3, C. phenolic resin and modified phenolic resin, D. stabilizer, E. pH regulator, F. thickener, G. leveling agent, H. film builder, I. wetting agent, J. antioxidant.

Description

Environment-friendly type galvanizing metal surface treating agent
Technical field
The present invention relates to a kind of chromium-free metal surface treatment agent, this metal conditioner can substitute the chromate-containing metal conditioner of common employing, especially substitute and the galvanized metal product is handled with chromate-containing metal conditioner, chromium-free metal surface treatment agent of the present invention is compared with chromate-containing treatment agent has more excellent rustless property, especially can prevent white rust for a long time.
Background of invention
Zinc in the metallic substance such as zinciferous Metal plating steel plate, aluminium sheet or aluminium is corrosion easily in atmosphere, produces the corrosion product that is called white rust, and this not only influences the outward appearance of metallic substance, but also the coating stopping property is had detrimentally affect.Usually the chromate treating that adopts is to use the metal conditioner that comprises chromic acid that these metallic substance are handled, and is the present widely used technical measures that are used to improve galvanized metal product rustless property.But, therefore press for a kind of metal conditioner of Chrome-free because the sexavalent chrome component has toxicity and carinogenicity.For example, contain the sexavalent chrome component that produces by chromate treating galvanized metal product in the chip owing to useless paint vehicle, therefore make to be difficult to chip is carried out waste treatment and recovery.
If being better than the chromium-free metal surface treatment agent of chromate treating agent, performance aspect cost, has advantage, then can avoid using the chromate treating agent to handle, and expect that this chromium-free metal surface treatment agent can help to prevent because the environmental pollution that ion caused that treatment agent produces.
Although use at present only contains the metal conditioner of a small amount of sexavalent chrome component or adopt the trivalent chromium component to substitute the metal conditioner of sexavalent chrome component, their performance performance is not good, and trivalent chromium can also be oxidized to sexavalent chrome.Therefore, using such metal conditioner only is a kind of transition method.
Several chromium-free metal surface treatment agents have been proposed at present, comprising applying steel plate galvanized with inorganic silicate, handle (as United States Patent (USP) 5108793) with organosilicon then, but still there are problems in they, its rustless property can't reach the effect that can reach with chromate-containing metal conditioner, in addition, the treatment solution stability does not reach requirement yet, and treatment process complexity, field procedure does not satisfy requirement yet, also has shortcomings such as other is bad such as film uniformity, treatment solution acid base pair workpiece is influential.Major cause is that the composition of these treatment solutions is too simple, and does not consider multiple influence factor, and particularly water-soluble silica gel and dispersed silica gel combine to the galvanized sheet role.
Summary of the invention
The objective of the invention is to solve the foregoing problems that prior art has, a kind of chromium-free metal surface treatment agent is provided and uses this metal conditioner to handle the method for metal material surface.By handling metal product, the especially surface of galvanized metal product, can obviously improve the rustless property of product with this metal conditioner; Especially aspect the rustless property of galvanized metal product, metal conditioner according to the present invention surmounts conventional chromate metal surface treatment agent effectively on cost; And metal conditioner of the present invention has excellent long term inhibition and gives birth to the white rust effect when being used for surface treatment galvanized metal product.The inventor has carried out conscientious repeatedly research, found that the chromium-free metal surface treatment agent that has claim 1 feature by use can solve the problem that prior art exists.
It is the silicon matter of solvent and as the polymer resol of main ingredient liquid that chromium-free metal surface treatment agent of the present invention comprises with water and a small amount of alcohol, described silicon matter comprises silicate and silicofluoride component, silica gel (water dispersion nano attitude) or/and the silicoorganic compound hydrolyzed oligomers component of following general formula (I), optional stablizer, pH regulator agent, thickening material, flow agent, film coalescence aid, wetting agent, the oxidation inhibitor of also containing of this metal conditioner.
Embodiment
In silicon matter of the present invention, comprise the silicate and the silicofluoride component of 0.5-3 weight part in per 100 weight parts, its effect is equivalent to the coating skeleton.Described silicate and silicofluoride are mainly water glass, pure aluminium silicate, zinc silicate, potassium silicate, Calucium Silicate powder, silicofluoric acid, zirconium silicate, Sodium Silicofluoride, lead silicate, sodium-potassium silicate, potassium silicofluoride, ferric metasilicate, Starso, lithium silicate, lithium metasilicate aluminium or polymerization metasilicic acid and receive.
Silicon matter of the present invention also comprises silica gel (water dispersion nano attitude) or/and the silicoorganic compound hydrolyzed oligomers component of following general formula (I):
Si nO mXR 1R 2R 3 (I)
Wherein,
The scope of n is generally 2-500,
The scope of m is generally 2-1000,
X represents heteroatoms, for example O, N, S,
R 1Expression replaces aliphatic group, does not replace aliphatic group, replaces aromatic group, does not replace aromatic group;
R 2Expression replaces aliphatic group, does not replace aliphatic group, replaces aromatic group, does not replace aromatic group;
R 3Expression replaces aliphatic group, does not replace aliphatic group, replaces aromatic group, does not replace aromatic group;
Above-described replacement situation is meant by common substituting group and replaces that these substituting groups for example are:
Hydroxyl, nitro, sulfonic group, halogen, for example fluorine, chlorine, bromine, iodine, C 1～C 18-alkyl, preferred C 1～C 12-alkyl, for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, amyl group, hexyl, 2-ethylhexyl, heptyl, octyl group, nonyl, decyl, dodecyl, 1,1-dimethyl dodecyl, C 2～C 18-thiazolinyl, preferred C 2～C 12-thiazolinyl, for example vinyl, propenyl, n-butene base, 2-methylpropenyl, pentenyl, hexenyl, 2-ethyl hexene base, heptenyl, octenyl, nonene base, decene base, laurylene base, 1,1-dimethyl laurylene base, C 2～C 18-alkynyl, preferred C 2～C 12-alkynyl, for example ethynyl, proyl, positive butynyl, 2-methyl-prop alkynyl, pentynyl, hexin base, 2-ethyl hexin base, heptyne base, octyne base, n-heptylacetylene base, decynyl, dodecyne base, 1,1-dimethyl dodecyne base, C 3～C 20-cycloalkyl, preferred C 3～C 12-cycloalkyl, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, ring octyl group, the carbon atom of these cycloalkyl can be replaced by above-described alkyl, thiazolinyl, alkynyl list or be polysubstituted, C 5～C 15-aryl for example can be replaced by above-described alkyl, thiazolinyl, alkynyl list or polysubstituted phenyl, naphthyl, anthryl etc., for example phenyl, o-tolyl, a tolyl, 1-naphthyl and 2-naphthyl, C 7～C 8-aralkyl, for example benzyl or 1-phenylethyl.
The effect of the siliceous oligopolymer component of above general formula (I) is as silica-based binding agent.Si nO mXR 1R 2R 3Can be nano level water dispersible silicide, also can be the polycondensation product by the organosilicon hydrolyzation gained.Its content is generally the 0.5-10 weight part of the described silicon matter of 100 weight parts.Can use the silica-based binding agent of the alcoholic solution of described alkoxysilane oligomer as chromium-free metal surface treatment agent of the present invention.
The preferred alkoxysilane oligomer of weight-average molecular weight (Mw) that use as 300-5000.If the weight-average molecular weight of alkoxysilane oligomer (Mw) is lower than 300, then the effect meeting variation of white rust is given birth in rust inhibition, particularly inhibition.If the weight-average molecular weight of alkoxysilane oligomer (Mw) is greater than 5000, then alkoxyl silicone ten thousand oligomer solutions become unstable, and gelling takes place easily.Obviously, if before applying gelling takes place, then the rustless property of metal conditioner can be badly damaged.As the starting raw material of described alkoxysilane oligomer, can use tetraethoxy, ethyl silicate 40, tetraethyl silicate 32, tetraethyl silicate 28, tetramethoxy-silicane, Trimethoxy silane, triethoxyl silane, two-(triethoxysilylpropyltetrasulfide) amine.
The present invention uses above-mentioned two class silicon matters, if the former is water-soluble, then the latter is a water dispersible, otherwise, if the former is a water dispersible, then the latter is water-soluble, the benefit of doing like this be at first water-soluble silica gel can with galvanized sheet with the non covalent bond bonding, form hydrophilic film, but this film is met the water capacity and is easily dissolved, and the interaction between this film and polymer resol and the paint film is relatively poor, if be covered hydrophobic dispersed silicon matter in the above, then can significantly improve the binding ability with polymer resol and paint film.Consider the stability problem of dispersed silicon matter in the aqueous solution, therefore, in metal conditioner of the present invention, also add special stabilizers especially, thereby can guarantee dispersed silicon matter and phenolic material no flocculation sediment phenomenon in a year, so just guaranteed quality product.
In chromium-free metal surface treatment agent of the present invention, the water that uses as the silicon matter solvent is deionized water, alcohol content is preferably 0.5-5 weight %, and described alcohol can be methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, amylalcohol, hexanol, hexalin, enanthol, n-Octanol, secondary octanol, nonanol-, nonylcarbinol, ethylene glycol, propylene glycol, butyleneglycol, pentanediol, hexylene glycol etc.Select the alcohol of opposed polarity and specific inductivity according to the difference of galvanized sheet being handled the back paint film.In general, the polarity of amino lacquer and pyroxylin(e)finish is less, and corresponding specific inductivity is also less, therefore need select polarity and the less alcohol of specific inductivity for this type of metal conditioner.Because the polarity of alkyd paint, polyurethane paint, acrylic paint, phenolic resin coating, epoxy resin-based paint raises successively, so the also rising successively of the polarity of the required solvent alcohol of metal conditioner, must consider the influence of surface tension and dipole moment in addition.
The resol that uses in metal finishing of the present invention and the polymerization degree of modified phenolic resins all do not surpass 200, water-soluble phenolic resin adhesive is made up of water soluble phenol resin and acetal, described water soluble phenolic fat is formed by phenol and formaldehyde, when the weight ratio of monohydric phenol in the phenol and dihydric phenol is 10 0: in the time of 5～30, water-soluble better.Modified phenolic resins comprises cyanurotriamide modified resol, quaternary ammonium salt-modified resol, rosin modified phenolic resin, lignin modification resol, chitin modified phenolic resins, starch conversion resol, polyvinyl alcohol modification resol, poly ethyldiol modified resol, acrylic amide modified resol.Described modified phenolic resins also needs to have certain solubleness, makes it can all dissolve after 30 minutes by ultra-sonic oscillation after adding solubility promoter such as alcohol etc. and tensio-active agent.Content is generally 0.2-5 weight %.
Can add multiple additives in Chrome-free galvanizing metal surface treating agent according to the present invention, these additives can be stablizer, pH regulator agent, thickening material, flow agent, film coalescence aid, wetting agent and oxidation inhibitor.Described stablizer can be a tensio-active agent, the complex composition of the complex composition of negatively charged ion and nonionic surface active agent or positively charged ion and nonionic surface active agent preferably, the standard of selecting is the size of its HLB value, usually, aniorfic surfactant can be selected from one or more in the hot sodium sulfonate of 1-, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, ox ester acid sodium and the sodium xylene sulfonate.Nonionic surface active agent can be selected from one or more in alkyl polyoxyethylene ether sodium sulfate, fatty alcohol-polyoxyethylene ether, alkylphenol polyoxyethylene, sorbester p18, sorbester p17, tween and the peregal usually.Cationic surfactant can be common quaternary ammonium salt.By weight, the content of these tensio-active agents is generally 1ppm-1%, is preferably 2ppm-0.5%, and more preferably 5ppm-0.2% most preferably is 10ppm-0.1%.
Chromium-free metal surface treatment agent according to the present invention is generally nearly neutrality, and the pH value can be in the 5-9 scope, and less to corrosion of metal like this, the user is more acceptant.Can use the pH regulator agent to regulate the pH value, described pH regulator agent comprises sodium hydroxide, yellow soda ash, sodium bicarbonate, potassium hydroxide, salt of wormwood, calcium hydroxide, lime carbonate, ammoniacal liquor, triethylamine, silicofluoric acid, hydrochloric acid, sulfuric acid, carbonic acid, hydrofluoric acid, oxalic acid, or the like.
Can in chromium-free metal surface treatment agent according to the present invention, add thickening material, thickening material can be a polyvinyl alcohol, carboxymethyl cellulose, Walocel MT 20.000PV, methacrylic ester and acrylate copolymer, polyurethane associative thickener, comprise the polyvinyl alcohol 15-88P/17-88P/24-88P that originates from Germany, the thickening material 638 that Wuxi City virtue rosy clouds chemical industry company limited produces, the Anke  HEUR-A polyurethane associative thickener that Hefei Anke Fine Chemicals Co., Ltd. produces, the JS-RHA thickening material that Shanghai Jinshan Chemical Co., Ltd. produces, the BE-903 thickening material that Bonn, Zhejiang chemical industry company limited produces, the thickening material that the good swallow chemistry of Changzhou company limited produces.By weight, the addition of thickening material is generally 0.00001%-1%, is preferably 0.0001%-0.5%.
Can add flow agent in chromium-free metal surface treatment agent according to the present invention, flow agent can be response type acrylate copolymer flow agent, modified organosilicon acroleic acid and/or the polyether(poly)urethane of polyether-modified dimethyl siloxane, response type Voncoat R 3310 flow agent, band carboxyl.By weight, the addition of described flow agent is generally 0.00001%-10%, is preferably 0.0005%-5%, more preferably 0.001%-0.5%.
Can add film coalescence aid in chromium-free metal surface treatment agent according to the present invention, film coalescence aid can be 12 lipidols, comprises the CS-12 of Japan, the TEXANOL of her gesture Man; The glycol monomethyl methyl esters, ethylene glycol monobutyl ether.By weight, the general preferred 0.0001%-0.4% of the addition of described film coalescence aid.
In chromium-free metal surface treatment agent of the present invention, solution can be with the solution of water as solvent.In this case, preferably there is improved wetting agent to add in the silica-based film-forming soln to handling the metal product wettability of the surface significant quantity.Chromium-free metal surface treatment agent institute galvanized sheet wettability of the surface to be processed is variation sometimes.If not processed dose of galvanized metal surfaces is wetting, just can not forms protective coating, and can not guarantee the rustless property on whole surface.Therefore need to add wetting agent, surface to be processed all obtains wetting like this.Wetting agent PM-WET100, PM-WET101, the PM-DI SPERSANT 5040 that can use organosilicon wetting agent, Pu Luomen company to produce; The GR-500 that lattice intercalation peaceful Chemical Industry Science Co., Ltd in Shanghai produces; The Richdol that Shang nautical mile specialization industry science skill company limited produces; Reg 101.By weight, the content of described wetting agent is 10ppm-0.1%.
Also contain oxidation inhibitor according to chromium-free metal surface treatment agent of the present invention, described oxidation inhibitor is selected from Resorcinol, Resorcinol, pyrocatechol, catechol, four [β-(3,5-di-t-butyl 4-hydroxy phenyl) propionic acid] pentaerythritol ester, 2,6-di-t-butyl-alpha, alpha-dimethyl amido Pyrogentisinic Acid, 4,4-methylene radical (2, the 6-DI-tert-butylphenol compounds), Tyox B, sodium pyrosulfate, Sodium Pyrosulfite, S-WAT, Sulfothiorine, thiocarbamide, halfcystine, methionine(Met), vitamins C and phosphite antioxidant, by weight, its content is 10ppm-0.1%.
The invention still further relates to a kind of metallic substance, the particularly surface treatment method of galvanized metal material, it is characterized in that, with the pH value for 5-9, be the silicon matter of solvent and be applied to metallic substance, especially galvanized steel product, particularly electro-galvanized steel product surface, drying, the thick coating of formation 10-100nm by comprising basically as the above-mentioned metal conditioner that the polymer resol of main ingredient liquid is formed with water and a small amount of alcohol.The method that is coated with this metal conditioner is not particularly limited, for example can uses pickling process, spraying method, rolling method etc.In addition, treatment temp, treatment time also are not particularly limited, can suitably select as the case may be.
In chromium-free metal surface treatment agent of the present invention, reach the effect that red rust and white rust are not given birth in long-term prevention by the coating that forms the thick metal conditioner of about 10-100nm.In addition, chromium-free metal surface treatment agent of the present invention does not have the peculiar defective of chromate treating product, that is, antirust function is impaired under about 70 ℃.And chromium-free metal surface treatment agent of the present invention can carry out drying in 5 ℃-150 ℃ wide temperature range, the advantage of bringing thus is that the thermal treatment of carrying out for the hydrogen embrittlement that prevents zinc-plated generation can be carried out simultaneously with the baking processing to metal conditioner.Coating method for galvanized workpiece can be undertaken by natural seasoning, cold air drying method or oven drying method.If chromium-free metal surface treatment agent of the present invention combines with electro-galvanizing, then thickness is about the rustless property that the thin anti-rust film of 10-100nm can have excellence.
In addition, the present invention is applicable to scribbling and comprises zinc powder and form finish paint on as the Chrome-free zinc rich paint of rust-stabilising pigment rather than galvanized product.The coating of metal conditioner also can be used for improving the rustless property on the conventional processing surface of galvanized metal product.
If the binder solution of made metal conditioner flocculates, then the rust inhibition of metal conditioner is often impaired.
Embodiment
Below by specific embodiment metal conditioner of the present invention is specifically described, but scope of the present invention is not so limited.
Embodiment 1-6 component is formed:
The component of the metal conditioner that adopts among the embodiment 1-6 is formed as shown in table 1, percentage shown in it
Number by weight.Table 1: product component percentage composition table
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6
Ethanol 5 5 4 4 2 2
Cyanurotriamide modified resol 1.5 0.5 1 1 1.5 1.5
Two-(triethoxysilylpropyltetrasulfide) amine 3 0 1 2 2.5 3
Silicon sol 0 3 3 2 1.5 1
Sorbester p17 (stablizer) 0.1 0.1 0.08 0.08 0.05 0.05
The pH value 6 6 6 6.5 6.5 6.5
Carboxymethyl cellulose (thickening material) 0.002 0.002 0.002 0.002 0.002 0.002
Acid-organosilicon crylic acid (flow agent) 0.02 0.02 0.02 0.02 0.02 0.02
Ethylene glycol monobutyl ether (film coalescence aid) 0.001 0.001 0.001 0.001 0.001 0.001
PM-WET100 (wetting agent) 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001
Catechol (oxidation inhibitor) 0.002 0.002 0.002 0.002 0.002 0.002
Deionized water Surplus Surplus Surplus Surplus Surplus Surplus
Clean and coating:
With the zinciferous Metal plating steel plate of 6cm * 4cm test specimen plate in " agent of Great quick deoiling ", cleaned 5 minutes down at 60 ℃.Use the clear water rinsing then 2 minutes, and in metal surface treating liquid of the present invention, soaked 2 minutes after 70 ℃ of warm air dryings, take out the back warm air drying, be coated with high basic acrylic polyester priming paint, film thickness: 10 μ m, acrylic acid top-coat film thickness: 5 μ m.
Test-results sees Table 2, table 3.
Erosion resistance: evaluation method is to handle but painted galvanized sheet not through the present invention, carries out 24 hours salt mist experiments.
Anti-finger printing: with Vaseline is human sweat's simulation medium, dips in the Vaseline that takes a morsel with clean soft cloth and evenly is applied to specimen surface, and the colour before and after the mensuration sample is smeared is poor.
Zero: expression colour difference Δ E is less than 2, and it is invisible to handle contact rear surface fingerprint.
*: as seen expression colour difference Δ E handles contact rear surface fingerprint greater than 2.
An adaptation (experiment of hundred lattice): cut on the galvanized sheet in japanning by cutting machine, depth of cut is with till reaching galvanized sheet material place, form the cubic grid of 100 1mm after, peel off by cellophane tape, estimate by the number of filming.
The secondary adaptation: the galvanized sheet of will painting floods after two hours in ebullient water, carries out and an identical evaluation of adaptation.
Anti-blackening: experimental technique is that the sample of 150mm * 75mm is vertically vertically put into boiling water along short transverse, and the height of half is exposed on water surface top, after the taking-up in a hour, measures the value of chromatism that front and back are handled on water surface top.Anti-blackening standard value be Δ E less than 8 (representing) with 0, Δ E is greater than 8 (usefulness * expressions).
Table 2: hot-dip galvanizing sheet steel
(Handan pot galvanize material SGH340-Z27, specification 75*1500*C) handles
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6
Erosion resistance (the salt-fog test white rust covered in 24 hours) ＞10％ ＞10％ ＜10％ ＜10％ ＜10％ ＜10％
Anti-finger printing × × ○ ○ ○ ○
An adaptation 78 71 100 99 99 96
The secondary adaptation 70 67 100 97 97 94
Anti-blackening × × ○ ○ ○ ○
Table 3: electrogalvanizing steel plate (Baosteel, model SECCN5, specification 0.60*1230*2236) is handled
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6
Erosion resistance (the salt-fog test white rust covered in 24 hours) ＞10％ ＞10％ ＜10％ ＜10％ ＜10％ ＜10％
Anti-finger printing × × ○ ○ ○ ○
An adaptation 80 79 100 100 98 96
The secondary adaptation 75 72 100 99 97 93
Anti-blackening × × ○ ○ ○ ○

Claims (10)

1. chromium-free metal surface treatment agent that is used to suppress corrosion, it is characterized in that, this metal conditioner is the silicon matter of solvent and forms as the polymer resol of main ingredient liquid by comprising with water and a small amount of alcohol basically, and described silicon matter comprises silicate and silicofluoride component, silica gel (water dispersion nano attitude) or/and the silicoorganic compound hydrolyzed oligomers component of following general formula (I):
Si nO mXR 1R 2R 3 (I)
Wherein,
The scope of n is generally 2-500,
The scope of m is generally 2-1000,
X represents heteroatoms, for example O, N, S,
R 1, R 2And R 3Expression replaces aliphatic group, does not replace aliphatic group, replaces aromatic group, does not replace aromatic group respectively,
Optional stablizer, pH regulator agent, thickening material, flow agent, film coalescence aid, wetting agent, the oxidation inhibitor of also containing of this metal conditioner.
2. according to the chromium-free metal surface treatment agent of claim 1, it is characterized in that, water is deionized water, alcohol content is 0.5-5 weight %, and alcohol is selected from methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, amylalcohol, hexanol, hexalin, enanthol, n-Octanol, secondary octanol, nonanol-, nonylcarbinol, ethylene glycol, propylene glycol, butyleneglycol, pentanediol and hexylene glycol.
3. according to the chromium-free metal surface treatment agent of claim 1 or 2, it is characterized in that, for polarity, less amino lacquer and the pyroxylin(e)finish of specific inductivity, select polarity and the less alcohol of specific inductivity, for the higher alkyd paint of polarity, polyurethane paint, acrylic paint, phenolic resin coating, epoxy resin-based paint, select the higher alcohol of polarity.
4. according to the chromium-free metal surface treatment agent of one of claim 1～3, it is characterized in that silicate in the solution and silicofluoride components contents are 0.5-3 weight %.Described silicoorganic compound hydrolyzed oligomers components contents is 0.5-10 weight %.
5. according to the chromium-free metal surface treatment agent of one of claim 1～4, it is characterized in that the polymerization degree of described resol and modified phenolic resins is no more than 200, content is 0.2-5 weight %.
6. according to the chromium-free metal surface treatment agent of one of claim 1～5, it is characterized in that described modified phenolic resins is selected from cyanurotriamide modified resol, quaternary ammonium salt-modified resol, rosin modified phenolic resin, lignin modification resol, chitin modified phenolic resins, starch conversion resol, polyvinyl alcohol modification resol, poly ethyldiol modified resol and acrylic amide modified resol.
7. according to the chromium-free metal surface treatment agent of one of claim 1～6, it is characterized in that, described stablizer is a tensio-active agent, the complex composition of the complex composition of preferred anionic and nonionic surface active agent or positively charged ion and nonionic surface active agent, aniorfic surfactant are selected from one or more in the hot sodium sulfonate of 1-, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, ox ester acid sodium, the sodium xylene sulfonate; Nonionic surface active agent is selected from one or more in alkyl polyoxyethylene ether sodium sulfate, fatty alcohol-polyoxyethylene ether, alkylphenol polyoxyethylene, sorbester p18, sorbester p17, tween or the peregal; Cationic surfactant is a quaternary ammonium salt, and by weight, the weight content of these tensio-active agents is 10ppm-0.1%.
8. according to the chromium-free metal surface treatment agent of one of claim 1～7, it is characterized in that, its pH value is in the 5-9 scope, and the pH regulator agent is selected from sodium hydroxide, yellow soda ash, sodium bicarbonate, potassium hydroxide, salt of wormwood, calcium hydroxide, lime carbonate, ammoniacal liquor, triethylamine, silicofluoric acid, hydrochloric acid, sulfuric acid, carbonic acid, hydrofluoric acid and oxalic acid.
9. according to the chromium-free metal surface treatment agent of one of claim 1～8, it is characterized in that, also contain thickening material, described thickening material is selected from polyvinyl alcohol, carboxymethyl cellulose, Walocel MT 20.000PV, methacrylic ester and acrylate copolymer, polyurethane associative thickener, the polyvinyl alcohol 15-88P/17-88P/24-88P that comprises Germany, Wuxi City virtue rosy clouds chemical industry company limited thickening material 638, the Anke  HEUR-A of Hefei Anke Fine Chemicals Co., Ltd. polyurethane associative thickener, the JS-RHA of Shanghai Jinshan Chemical Co., Ltd. thickening material, the good swallow chemistry of Bonn, the Zhejiang BE-903 of chemical industry company limited thickening material and Changzhou company limited thickening material, addition is 0.0001 weight %-0.5 weight %.
10. according to the chromium-free metal surface treatment agent of one of claim 1～9, it is characterized in that, also contain flow agent, described flow agent is selected from response type acrylate copolymer flow agent, modified organosilicon acroleic acid and the polyether(poly)urethane of polyether-modified dimethyl siloxane, response type Voncoat R 3310 flow agent, band carboxyl, and addition is 0.0001 weight %-0.5 weight %.
CN200710010966A 2007-04-10 2007-04-10 Environment-friendly type galvanizing metal surface treating agent Expired - Fee Related CN100584908C (en)

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CN102147576B (en) * 2010-02-09 2013-02-20 京东方科技集团股份有限公司 Photoresist stripping liquid composition
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US8557384B2 (en) 2008-02-21 2013-10-15 Dupont Teijin Films U.S. Limited Partnership Silicate-containing antifog coatings
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CN102827504A (en) * 2012-09-18 2012-12-19 杨东佑 Anticorrosion liquid for metal surface corrosion resistance, and preparation method and anticorrosion treatment method thereof
CN103087629A (en) * 2012-12-18 2013-05-08 芜湖恒坤汽车部件有限公司 Anti-corrosion metal surface silane treatment agent and preparation method thereof
CN103088327A (en) * 2012-12-18 2013-05-08 芜湖恒坤汽车部件有限公司 Metal surface silane treatment agent containing water-soluble phenolic resin and preparation method thereof
CN103087630A (en) * 2012-12-18 2013-05-08 芜湖恒坤汽车部件有限公司 Metal surface silane treatment agent containing monoethanolamine benzoate and preparation method thereof
CN103397327A (en) * 2013-07-22 2013-11-20 江苏博业涂装工程有限公司 Waterborne sealing agent for zinc-based micro coating and preparation method of waterborne sealing agent
CN103397327B (en) * 2013-07-22 2015-12-02 江苏博业涂装工程有限公司 For watersoluble closed dose of the micro-coating of zinc-base and preparation method thereof
CN103435365A (en) * 2013-08-09 2013-12-11 中交第二航务工程局有限公司 Organic polymer pasty fluid for electrochemical desalting and preparation method
CN103694857A (en) * 2013-11-29 2014-04-02 明光市留香泵业有限公司 Water-based inter-process environment-friendly antirust liquid and preparation method thereof
CN103882416A (en) * 2014-03-26 2014-06-25 北京大学深圳研究院 Zirconium metal painting pre-treatment agent for scrubbing cold-roll steel sheets
CN104099650B (en) * 2014-08-01 2018-03-20 广东富行洗涤剂科技有限公司 A kind of dehydrating agent
CN104099650A (en) * 2014-08-01 2014-10-15 东莞市富行洗涤剂科技有限公司 Dehydrator
CN104448999A (en) * 2014-11-18 2015-03-25 厦门建霖工业有限公司 Anti-fingerprint surface treating agent and use method thereof
CN104498922A (en) * 2014-12-31 2015-04-08 芜湖华金冲压加工件厂 Surface treatment agent for stainless steel sheets in sheet metal process
CN104498929A (en) * 2014-12-31 2015-04-08 芜湖华金冲压加工件厂 Protection method of stainless steel plate in sheet metal process
CN104480456A (en) * 2014-12-31 2015-04-01 芜湖华金冲压加工件厂 Preparation method of surface treating agent used for stainless steel sheet in sheet metal process
CN104480456B (en) * 2014-12-31 2017-02-22 芜湖华金冲压加工件厂 Preparation method of surface treating agent used for stainless steel sheet in sheet metal process
CN107969132B (en) * 2015-04-24 2020-08-25 日本帕卡濑精株式会社 Aqueous surface treatment agent, method for producing coating film, and surface-treated material
CN107969132A (en) * 2015-04-24 2018-04-27 日本帕卡濑精株式会社 Water system surface conditioning agent, the manufacture method of overlay film and surface treated material
CN107299338B (en) * 2017-07-09 2019-04-12 无锡市恒利弘实业有限公司 A kind of steelwork aqueous, environmental protective antirust agent and its preparation method and application
CN107299338A (en) * 2017-07-09 2017-10-27 无锡市福吉电子科技有限公司 A kind of steelwork aqueous, environmental protective antirust agent and its preparation method and application
CN109609940A (en) * 2019-01-10 2019-04-12 廊坊师范学院 The preparation method and workpiece silicidation technique of metalwork wear resistence silication liquid
CN110257830A (en) * 2019-07-11 2019-09-20 浙江九合金属表面处理技术有限公司 Galvanized sheet inorganic agent
CN112791924A (en) * 2019-12-30 2021-05-14 廊坊京磁精密材料有限公司 Surface treatment method for neodymium iron boron permanent magnet material and permanent magnet material product
CN111570237A (en) * 2020-05-27 2020-08-25 四川金城栅栏工程有限公司 Fence anticorrosion process and anticorrosion fence produced by same
CN112082043A (en) * 2020-07-22 2020-12-15 石家庄常丰环境工程有限公司 Pipeline anticorrosive coating and spraying method thereof
CN112845279A (en) * 2020-12-24 2021-05-28 太仓小熊精密模具有限公司 Environment-friendly energy-saving novel metal cold forming processing method

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