CN102719118A - Antirust paint - Google Patents
Antirust paint Download PDFInfo
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- CN102719118A CN102719118A CN2012101928441A CN201210192844A CN102719118A CN 102719118 A CN102719118 A CN 102719118A CN 2012101928441 A CN2012101928441 A CN 2012101928441A CN 201210192844 A CN201210192844 A CN 201210192844A CN 102719118 A CN102719118 A CN 102719118A
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Abstract
The invention relates to an antirust paint composition which comprises the following components by mass percent: 2-20% of organosilicon compound, 3-4% of aluminum chloride, 20-60% of metal powder of one or more than two of zinc powder, zinc alloy powder and aluminum powder, 0.1-2% of rare earth compound, and the balance of organic solvent. The paint film formed by the antirust paint composition has good corrosion resistance.
Description
Technical field
The present invention relates to anticorrosive coating composition and have the member manufacturing method of the anti-rust coating that uses said composition.At length say, relate to the coating composition of filming of the excellent corrosion resistance that can form the film that for example goes for precision instrument or automobile impact briquetting steel plate etc. and have the member manufacturing method of the anti-rust coating that uses said composition.
Background technology
The antirust of parts to have metallic surfaces such as iron and steel is the coating of purpose, mostly uses with zinc powder and the chromic acid coating as staple.This coating can keep the stability of zinc powder for a long time through the passivity effect of 6 valency chromium, liquid excellent storage stability.In addition, film,, therefore can prevent corrosions of metal such as bottom iron and steel, obtain excellent rust-proof effect because well-known zinc can be brought into play alternative corrosive nature effectively by what the coating that contains this zinc powder formed.
But, because the hazardous property of 6 valency chromium has caused the worry of environmental pollution, human health damage, quickening to promote to use legally the rules and regulations of poisonous metals such as 6 valency chromium in recent years.Receive the influence of this trend, a lot of industries are not all used the problem of poisonous metals such as 6 valency chromium fully in investigation.Therefore, the rust proof paint field also consumingly expectation the coating of poisonous metal such as chromium appears not containing fully.
As a this example that does not contain the rust proof paint of chromium, a kind of coating that zinc powder and binder constituents are dispersed or dissolved in organic solvent is arranged, be high density zinc powder coating.Contain organic system and inorganic system in the binder constituents of this high density zinc powder coating.From the viewpoint of weather resistance is that the inorganic system of tackiness agent is comparatively excellent with silicoorganic compound, for example, in the multiple-anticorrosion erosion spraying of boats and ships or bridge, uses as priming paint.
But inorganic is that high density zinc powder coating is easy to generate space part (cavity) in film.In addition, be difficult to control the thickness of filming.In order to overcome these shortcomings, following technology is disclosed.
Patent documentation 1 discloses the technology that diameter is the palpus crystalline lime carbonate of 20～30 μ m that contains of replenishing.In this technology, the palpus crystalline substance of interpolation have the function that prevents to produce the film crackle.
In addition, patent documentation 2 discloses and used the ratio of weight-average molecular weight/number-average molecular weight is the alkyl silicate resin below 40, and the morpholine gel time of coating is the high density zinc powder coating below 60 seconds.Document explanation is because this coating setting time is fast, therefore suppressed the crack development and with being communicated with of space.
The disclosed technology of above-mentioned patent documentation, though effective really for the high density zinc powder coating of thick film, can not provide and can stablize the film that forms about 10 μ m and its and film and have the coating of higher erosion resistance.With this film is that the main application that high corrosion resistance is filmed is office apparatus, electric power apparatus, automobile etc.; Specifically can the give an example union piece of bolt or nut etc.; The fixer of clamp, clamping plate etc., the moulded section article of metal sheet, clamshell, hinge, switchboard etc. etc.These parts, not only assembly precision is strict, and owing to when processing or assembling, bear stronger shearing force mostly, and self intensity or the clinging power of therefore filming needs higher level.
An effective means that satisfies this demand is the high temperature sintering of filming.But; The sintering conduct is there to be the words of technological high density zinc powder coating under the high temperature about 300 ℃; The silicoorganic compound that constitute tackiness agent sharply shrink; Even use the disclosed technology of above-mentioned patent documentation can not prevent the development of interior crackle of filming, even the situation that in being processed parts, produces fracture is arranged.
Patent documentation 3 discloses a kind of rust proof paint; Also can not form the film that is difficult to crack even it does not use poisonous metal compounds such as chromium at high temperature to carry out sintering processes, it can form film and anti-rust coating excellent corrosion resistance about 10 good μ m of surface shape.This anticorrosive coating composition, contain the silicoorganic compound that account for all compsn 5～40 quality %, 0.05～5.0 quality % the organic titanate compound, from zinc powder, Zinc alloy powder, and the cohort that constitutes of aluminium powder select metal-powder and the organic solvent of 10～60 quality % of one or more 20～60 quality %.
But along with the further needs of producing, need more high performance filming, so the applicant further improves to it on the basis of patent documentation 3 and has obtained the present invention.
Patent documentation 1: japanese kokai publication hei 11-293200 communique
Patent documentation 2: TOHKEMY 2004-359800 communique
Patent documentation 3:CN101925659A.
Summary of the invention
The purpose of this invention is to provide a kind of anticorrosive coating composition and a kind of method with parts that protection against corrosion films of using its anticorrosive coating composition of making is provided.
According to the present invention, contain the tackiness agent and the metal-powder of non-water system through use, the tackiness agent of non-water system uses the solution that contains silicoorganic compound and aluminum chloride, rare earth compound can solve above-mentioned problem.
As the anticorrosive coating composition that an embodiment of the invention provide, contain the silicoorganic compound that account for all compsn 2～20 quality %, 3～4 quality % aluminum chloride, from zinc powder, Zinc alloy powder, and the cohort that constitutes of aluminium powder select metal-powder, the rare earth compound of 0.1-2 quality % and the organic solvent of surplus of one or more 20～60 quality %.
As the member manufacturing method with anti-rust coating that another embodiment of the invention provides, it contains following operation:
Described anticorrosive coating composition is coated the lip-deep painting process that comprises this metallic surface with metallic surface parts;
This coating anticorrosive coating composition is heated to 200～400 ℃ of heating processes that form anti-rust coating.
Preferred implementation such as following (a)～(d) in anticorrosive coating composition of the invention described above and the method for manufacture.
(a) silicoorganic compound in the above-mentioned anticorrosive coating composition are one or more compounds of from the cohort that tetraalkyl silicate compound with carbonatoms alkyl below 3 and oligopolymer thereof constitute, selecting.
(b) rare earth compound in the above-mentioned anticorrosive coating composition is the compound of lanthanum, cerium.
(c) metal-powder in the above-mentioned anticorrosive coating composition is lepidiod.
(d) surface of the above-mentioned anti-rust coating of formation is the surface of iron and steel parts.
Anticorrosive coating composition of the present invention does not contain each and waits the poisonous metal compound.Therefore, need not worry environmental pollution or the health of human body worked the mischief.And working lipe is long, easily operation.
In addition, can form the film about 10 good μ m of surface shape, handle even this film is carried out high temperature sintering, in film, also be not easy to produce big crackle, erosion resistance is extremely excellent.
Embodiment
Below, specify these compositions, anticorrosive coating composition inflation method, and use the method for manufacture of the anti-rust coating of this anticorrosive coating composition.In addition, in the explanation of following anticorrosive coating composition, short of special appointment % then is the quality % that accounts for whole anticorrosive coating compositions.
(1) silicoorganic compound
As the binder constituents in the anticorrosive coating composition of the present invention,, use silicoorganic compound, aluminum chloride, rare earth compound in order in the pyritous sintering processes, not produce big crackle.
Wherein, silicoorganic compound from the cohort that organoalkoxysilane and hydrolyzate thereof constitute, select one or more form.
The concrete example of organoalkoxysilane; Can give an example tetramethoxy-silicane, tetraethoxysilane, methyltrimethoxy silane, Union carbide A-162, vinyltrimethoxy silane, vinyltriethoxysilane, γ-Racemic glycidol oxygen propyl trimethoxy silicane etc., but be not limited to this.Can use commercially available various organoalkoxysilanes as silane coupling agent.
In these organoalkoxysilanes, preferably tetraalkoxysilane or their oligopolymer such as tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, especially good is carbonatoms is below 3 tetraalkoxysilane or their oligopolymer.When causing condensation reaction through sintering processes, can form filming of three-dimensional crosslinking structure, improve coating strength easily.In addition, the volumetric shrinkage during owing to condensation is fewer, is not easy to generate crackle.
The content of above-mentioned silicoorganic compound preferably is controlled at 2～20% of whole anticorrosive coating compositions.During less than 2%, the trend of coating strength step-down is arranged, the words that content further reduces cause metal-powder to produce the decline of tangible space part (inner chamber) erosion resistance each other.On the other hand, its content is greater than 20%, because the dispersion density loss of the metal-powder in the anti-rust coating relatively, erosion resistance has a declining tendency.Especially good scope is 10～15%.
(2) aluminum chloride
Anti-rust coating of the present invention in order to reach the purpose that improves coating characteristic, contains aluminum chloride.Aluminum chloride preferably adopts Aluminum chloride anhydrous.
The content of aluminum chloride preferably is controlled at 3～4% in anhydrous form.The very few words of aluminum chloride can not play one's part to the full, and can not get its effect, and therefore, the erosion resistance of anti-rust coating has a declining tendency.On the other hand, superfluous, that corrosive nature rises not obvious, and the better scope of the content of aluminum chloride is 3.5.
(3) metal-powder
The metal-powder that contains in the anti-rust coating of the present invention, by from always be used in high density zinc dust anticorrosive primer, zinc powder, zinc alloy metal powder, and the cohort of aluminium powder select one or more to constitute.As the example of zinc alloy can give an example Zn-Ni, Zn-Sn, Zn-Fe, Zn-Al, Zn-Al-Mg etc.
The content of metal-powder preferably is controlled in 20～60% the scope in the anticorrosive coating composition, is more preferably 30～50%.It is difficult that the coating of the film like of the words anticorrosive coating composition that content is too much becomes, simultaneously the strength degradation of anti-rust coating.On the contrary, if content is very few, crackle develops easily, and the whole erosion resistance of filming descends.
Even it is in order to make the thickness attenuation of anti-rust coating also have higher erosion resistance, preferably lepidiod as the shape of the metal-powder of the raw material of anticorrosive coating composition.With flakey, can be implemented in the anti-rust coating metal-powder at the structure of thickness direction lamination.This lamination structure even because the contraction that the polymerization of binder constituents causes causes in anti-rust coating, cracking, also can suppress its development, prevents to produce and exposes the big crackle that is processed the sort of degree of parts.
The mean thickness at scaled metal powder end is 1/200～1/2 of an anti-rust coating mean thickness, and the MV of the diameter of the metal-powder length of long part (lepidiod) 1/20～10 times of mean thickness of metal-powder preferably.Even in the coating condition because of anticorrosive coating composition is to produce on the thickness of filming under the condition of deviation, after also can stably suppress to crack when carrying out sintering processes in the heat treated stated.The better scope of the mean thickness of metal-powder is 1/200～1/10 of an anti-rust coating mean thickness, if especially good 1/200～1/20.The better scope of the MV of the diameter of metal-powder is 1/10～5 times of mean thickness of metal-powder, and is especially good 2/5～2 times words.
For example film when being the 10 μ m left and right sides, the metal-powder of the scope that this is best is that lepidiod mean thickness is 0.05～5 μ m, and the MV of diameter is 0.5～100 μ m.Better the metal-powder of scope is that lepidiod mean thickness is 0.05～1 μ m, and the MV of diameter is 1～50 μ m.The metal-powder of especially good scope is that lepidiod mean thickness is 0.05～0.5 μ m, and the MV of diameter is the scope of 4～20 μ m.
Lepidiod mean thickness has the worry that causes its fracture easily than above-mentioned scope hour when the stirring in the modulation of anticorrosive coating composition, married operation.The metal-powder fracture is difficult to keep flakey, possibly be difficult to obtain the lamination structure.On the other hand, bigger than above-mentioned scope, cause being difficult to obtain the structure of a plurality of lamination metal-powders at the anti-rust coating thickness direction, worry that the effect that suppresses crack growth has the trend that weakens.
The MV of diameter is difficult to obtain the structure of scaled metal powder end lamination than above-mentioned scope hour in anti-rust coating, worry that the effect that suppresses crack growth has the trend that weakens.On the other hand, when bigger, in anti-rust coating, possibly cause the sparse of metal-powder distribution than above-mentioned scope.
The ratio of the forming when metal-powder in the anticorrosive coating composition is made up of a plurality of kinds does not have particular restriction, but when more paying attention to erosion resistance, preferably contains zinc powder or Zinc alloy powder.From improving the ratio that viewpoints such as appearance characteristics improve aluminium powders is favourable, even but the words that contain zinc powder or Zinc alloy powder this moment also are gratifying from the viewpoint of erosion resistance.
(4) rare earth compound
Anticorrosive coating composition of the present invention, rare earth compound are preferably selected from the rare earth compound of lanthanum, cerium, for example: Cerium II Chloride, cerous nitrate.
The content of rare earth compound preferably is controlled at 0.1～2% in anhydrous form.The words of the very few less than 0.1% of rare earth compound can not play one's part to the full, and can not get its effect, and therefore, the erosion resistance of anti-rust coating has a declining tendency.On the other hand, superfluous above 2%, that corrosive nature rises not obvious, and the better scope of the content of aluminum chloride is 0.5-1.
(5) organic solvent
Anticorrosive coating composition of the present invention makes its words that contain organic solvent then better to the liquid infiltration that is processed parts when in the coating operation, can access higher the filming of binding property.In addition, contain organic solvent through making it, the dispersiveness of the various compositions that add in the time of coating can being improved.Therefore the homogeneity of anticorrosive coating composition increases.
As the suitable organic solvent alcohols such as methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, hexanol, methoxybutanol, methoxymethyl butanols of can giving an example; The ester class of the acetic ester of these alcohols, propionic ester etc.; Glycolss such as terepthaloyl moietie, Diethylene Glycol, triethylene glycol, polyoxyethylene glycol, Ucar 35, dipropylene glycol, tripropylene glycol, and ethers such as the methyl ether of these glycol, ethyl ether, butyl ether.In addition, hydrocarbons such as toluene, YLENE, mineral turpentine, solvent naphtha can use.Above-mentioned these both can use the mixture that also can be used as several kinds to use separately.
(6) other additives
Anticorrosive coating composition of the present invention can contain the various additives that in coating, usually use on demand.As such additive, the tackifier of can giving an example, rust-stabilising pigment, silica colloidal particulate etc.
As the example of tackifier can give an example fatty acid amine, polymeric amide, oxidic polyethylene, hydroxypropylcellulose, or silicate is inorganic tackifier.
As the example of rust-stabilising pigment can give an example zn phosphate, trimagnesium phosphate, zinc molybdate, molybdic acid aluminium etc.
So-called silica colloidal particulate is that particle size is the gelationus silicon dioxide granule of fine liquid below about 1 μ m, and is identical with above-mentioned silicon compound, has to improve the erosion resistance of filming and the effect of coating strength.The coating commonly used such as wetting agent, skimmer that in anti-rust coating of the present invention, also can contain other is used additive.
These other content of additive, summation preferably is controlled at 0.1～10% scope.During less than 0.1%, worry can not get the effect of additive, the words above 10% relatively descend as the metal-powder of main agents or the content of binder constituents, worry to have a declining tendency as the erosion resistance of fundamental characteristics.
In addition, each composition of above-described formation anti-rust coating of the present invention can use one or two or more.
(7) method of manufacture of the adjustment of anticorrosive coating composition, anti-rust coating etc.
Anticorrosive coating composition of the present invention through above-mentioned each composition is stirred fully, mixes, is evenly dispersed in the liquid metal-powder and modulates.
The parts that are processed that are suitable for this anticorrosive coating composition can be any parts with metallic surface.Both can be metallic substance, also can be that its surperficial at least a portion is the metallic substance of metal and for example resin and ceramic matrix material.The non-metallic component of the resin component that perhaps, also can be at least a portion surface be metallized through electroplating processes etc. etc.Even in such parts, contain ferrous material is that steel etc. also are fine.Steel surface can apply widely used processing as preceding processing such as the application of the Shot Blasting that is used to improve binding property and erosion resistance, phosphate coating film processing etc.Perhaps; Also can carry out electrolytic zinc electroplating processes or electrolytic zinc alloy (Zn-Sn at steel surface; Zn-Fe, Zn-Ni etc.) electroplating processes or fused zinc electroplating processes, molten zinc alloy electroplating processes or hot dip alloyed zinc electroplating processes (below, these are referred to as " zinc is electroplating processes ") etc.But,, even be process object therefore, can realize that also with having carried out zinc be that the surface of electroplating processes is the identical erosion resistance of process object with the surface of steel itself because compelx coating of the present invention has excellent barriering effect.Thereby, when paying attention to productivity etc., be that the method for process object is favourable with the surface of steel itself.
Form to parts does not have particular restriction, is that example describes with steel, from steel plate, reinforcing bar, steel pipe, the steel ingot widget to molding to bolt etc., can both be suitable for pantomorphic parts.
To the coating of the anticorrosive coating composition that is processed parts, can carry out through for example rolling coating, spraying, bristle coating, spin coating, dipping domestic methods such as (dip-coatings), can be according to the suitable coating process of the morphology selection of parts.Be that the scope of 2～30 μ m is coated with the coating thickness that forms after the heat treated be gratifying.Preferably be controlled at 5～20 μ m from the viewpoint coating thickness of erosion resistance and binding property or secondary workability compatibility, the words that are controlled at 7～15 μ m are especially good.In addition, to the no particular restriction of liquid temperature of bed material agent in this painting process.Usually can carry out with normal temperature.
Heat treated after the coating (sintering) is preferably in 200～400 ℃ carries out, and is especially good 250～350 ℃ words.Treatment time also depends on coating thickness, if the scope of 2～30 μ m preferably is controlled to be 10～120 minutes scope.In addition, before this heat treated, for drying also can preheat.Through preheating, can suppress the deviation of the temperature in the heat treated thereafter.Help to improve erosion resistance like this.Therefore, when especially pursue improving the quality of compelx coating, preheat and have effective possibility.Pre-heating temperature preferably is controlled to be 80 ℃～120 ℃ scope, and the words that are controlled at 100 ℃～120 ℃ scope are especially good.The pre-warmed time should determine with the thickness of filming aptly, but if the scope of 2～30 μ m preferably was controlled at 5～20 minutes.But, even the present invention does not carry out such preheat processing and accessing erosion resistance identical when carrying out yet, therefore when paying attention to because the interpolation of operation causes the influence that productivity descends, still do not carry out this preheat comparatively favourable.
Embodiment
Below utilize embodiment that the present invention is described in further detail, carry out but scope of the present invention is not limited to these embodiment.
According to the proportioning shown in the table 1 (quality percentage composition), use coating each composition to be stirred 3 hours together with impeller, obtain coating composition.
Then, on degreasing in advance, clean carbon steel sheet,, carry out 280 ℃ * 30 minutes heat treated, form the anti-rust coating of thickness 10 μ m with each coating of scraping strip coating machine coating.
[table 1]
Use is whenever carried out the evaluation of the erosion resistance of this antirust processing steel plate at a distance from 50 hours inspection outward appearances according to the salt spray testing of JIS-Z2371 regulation.Standard with range estimation judges whether to have produced red embroidery, is judged as the upper limit of the erosion resistance of protective membrane the stage of seeing red embroidery more than 1% of waiting to try steel plate.
In addition, under the state of adjusted 50 ℃ of humidity 65%, preserve coating, the gel determination of carrying out coating obtains the working lipe of coating up to the time that tangible viscosity rising occurs.
Can find out from table 1, the coating of embodiments of the invention 1～3, not only thickness is 10 μ m, and has shown high rust-preventing characteristic.
Applicant's statement; The present invention explains detailed process equipment of the present invention and technical process through the foregoing description; But the present invention is not limited to above-mentioned detailed process equipment and technical process, does not mean that promptly the present invention must rely on above-mentioned detailed process equipment and technical process could be implemented.The person of ordinary skill in the field should understand, and to any improvement of the present invention, to the interpolation of the equivalence replacement of each raw material of product of the present invention and ancillary component, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.
Claims (6)
1. rust proof paint constituent, contain the silicoorganic compound that account for all compsn 2～20 quality %, 3～4 quality % aluminum chloride, from zinc powder, Zinc alloy powder, and the cohort that constitutes of aluminium powder select metal-powder, the rare earth compound of 0.1-2 quality % and the organic solvent of surplus of one or more 20～60 quality %.
2. rust proof paint constituent according to claim 1; It is characterized in that said silicoorganic compound are one or more compounds of from the cohort that the tetraalkyl silicate compound with carbonatoms alkyl below 3 and oligopolymer thereof constitute, selecting.
3. rust proof paint constituent according to claim 1 and 2 is characterized in that, said rare earth compound is the compound of lanthanum, cerium.
4. according to each described rust proof paint constituent in the claim 1～3, it is characterized in that said metal-powder is lepidiod.
5. method of manufacture with member of anti-rust coating, contain following operation:
Each described rust proof paint constituent in the claim 1～4 is coated the lip-deep painting process that comprises this metallic surface of member with metallic surface;
This coating rust proof paint constituent is heated to 200～400 ℃ of heating processes that form anti-rust coating.
6. the method for manufacture with member of anti-rust coating according to claim 5 is characterized in that, the surface of the said anti-rust coating of formation is the surface of steel and iron member.
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| CN201210192844.1A CN102719118B (en) | 2012-06-12 | 2012-06-12 | A kind of antirusting paint |
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| CN201210192844.1A CN102719118B (en) | 2012-06-12 | 2012-06-12 | A kind of antirusting paint |
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| CN103433482A (en) * | 2013-07-31 | 2013-12-11 | 江苏麟龙新材料股份有限公司 | La-Ce-containing flaky-shaped multi-component aluminum, zinc and silicon alloy powder and preparation method of alloy powder |
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| CN103965700A (en) * | 2014-05-20 | 2014-08-06 | 潜山县新型工程建筑材料有限公司 | Composite phosphate anti-rust pigment |
| CN108893049A (en) * | 2018-06-07 | 2018-11-27 | 邵延荣 | A kind of anticorrosive coating composition |
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| CN103433480A (en) * | 2013-07-31 | 2013-12-11 | 江苏麟龙新材料股份有限公司 | La-Pr-Nd-containing flaky-shaped multi-component aluminum, zinc and silicon alloy powder and preparation method of alloy powder |
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| CN103433482B (en) * | 2013-07-31 | 2015-10-21 | 江苏麟龙新材料股份有限公司 | Scale-like multi-component zinc aluminum silicon alloy powder containing La and Ce and preparation method thereof |
| CN103614070A (en) * | 2013-11-20 | 2014-03-05 | 湖州中辰建设有限公司 | Organic silicone heat-resisting anticorrosive paint |
| CN103834302A (en) * | 2014-03-19 | 2014-06-04 | 浙江红高梁木业有限公司 | High-temperature-resistant coating for steel door and preparation method of high-temperature-resistant coating |
| CN103965700A (en) * | 2014-05-20 | 2014-08-06 | 潜山县新型工程建筑材料有限公司 | Composite phosphate anti-rust pigment |
| CN108893049A (en) * | 2018-06-07 | 2018-11-27 | 邵延荣 | A kind of anticorrosive coating composition |
| CN113993638A (en) * | 2019-07-03 | 2022-01-28 | 中国涂料株式会社 | Heat-resistant coating composition, heat-resistant coating film, substrate with heat-resistant coating film, and method for producing same |
| CN110746822A (en) * | 2019-11-25 | 2020-02-04 | 苏州市相城区望亭镇天瑞机械配件加工厂 | Antirust coating for automobile transmission shaft |
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