CN104059489B - A kind of metal surface chemical pretreatment solution and its production and use and hot-dip metal plated material - Google Patents
A kind of metal surface chemical pretreatment solution and its production and use and hot-dip metal plated material Download PDFInfo
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Abstract
The invention provides the preparation method of a kind of metal surface chemical pretreatment solution, the method comprises water, silane coupler, water-soluble silicate, promoter, cilicon oxide filler and water-soluble film-forming resin is mixed successively. The present invention also provides the metal surface chemical pretreatment solution for preparing according to preparation method as above and above-mentioned metal surface chemical pretreatment solution in the purposes of preparing in metal material. The present invention also provides a kind of hot-dip metal plated material, and this hot-dip metal plated material comprises hot-dip metal plated base material and be attached to the coating on this hot-dip metal plated base material, and described coating is the cured product of metal surface as above chemical pretreatment solution. The corrosion resistance of the protecting film that metal surface provided by the invention chemical pretreatment solution forms is very good. In addition, the storage endurance of metal surface provided by the invention chemical pretreatment solution is very excellent, can at room temperature store 180 days and obvious proterties does not occur change and hydraulic performance decline after preparation completes.
Description
Technical field
The present invention relates to metal protection field, particularly, relate to the preparation method of a kind of metal surface chemical pretreatment solution, byThe metal surface chemical pretreatment solution that this preparation method obtains, the purposes of this metal surface chemical pretreatment solution and hot-dip metal plated material.
Background technology
Hot-dip metal plated material, comprises hot-dip galvanized metal material and hot-dip aluminizing zinc metal material, in order to prevent corrosion, allCan be at the surface of hot-dip metal plated material coating layer of metal chemical surface treatment liquid to form protecting film. Thereby metal surface chemistryThe performance for the treatment of fluid is very important for the anti-corrosion of hot-dip metal plated material.
For example, CN101608306A discloses a kind of passivating solution, also belongs to a kind of metal surface chemical pretreatment solution, its featureBe, this passivating solution is the aqueous solution that contains water-soluble molybdenum compound, boric acid, water soluble organic substance and Ludox, wherein, described inWater soluble organic substance is the mixture of alcohol and organic carboxyl acid.
But the corrosion resistance that experiment showed, the protecting film that this metal surface chemical pretreatment solution forms is still poor.
Summary of the invention
The corrosion resistance that the object of the invention is the protecting film that overcomes the chemical pretreatment solution formation of existing metal surface is poorDefect, provides a kind of metal surface chemical pretreatment solution that can form the good protecting film of corrosion resistance.
To achieve these goals, the invention provides the preparation method of a kind of metal surface chemical pretreatment solution, the methodComprise water, silane coupler, water-soluble silicate, promoter, cilicon oxide filler and water-soluble film-forming resin are mixed all successivelyEven; Described silane coupler comprises the first silane coupler and the second silane coupler, and described the first silane coupler is R-Si(OCH3)3、R-Si(OC2H5)3、R-SiCH3(OCH3)2And R-SiCH3(OC2H5)2In at least one, and R selects independently of one anotherFrom NH2(CH2)2NH(CH2)3-、NH2(CH2)2NHCH2CH(CH3)CH2-、HO(CH2)2NH(CH2)2NH(CH2)3-or NH2(CH2)2NH(CH2)2NH(CH2)3-; Described the second silane coupler is Cl (CH2)3Si(OCH3)3、Cl(CH2)3Si(OC2H5)3、Cl(CH2)3SiCH3(OCH3)2And Cl (CH2)3SiCH3(OC2H5)2In at least one; Described promoter is thiocarbamide and/or urea.
The present invention also provides the metal surface preparing according to preparation method as above chemical pretreatment solution.
The present invention also provides above-mentioned metal surface chemical pretreatment solution in the purposes of preparing in metal material.
The present invention also provides a kind of hot-dip metal plated material, and this hot-dip metal plated material comprises hot-dip metal plated base material and is attached toCoating on this hot-dip metal plated base material, described hot-dip metal plated base material is galvanizing metal base, hot-dip aluminizing zinc metal base and heatAt least one in aluminum-zinc alloy magnesium metal base material, is characterized in that, described coating is metal surface as above chemical treatmentThe cured product of liquid.
By technique scheme, the corrosion resistance ten of the protecting film that metal surface provided by the invention chemical pretreatment solution formsDivide good. In addition, the storage endurance of metal surface provided by the invention chemical pretreatment solution is very excellent, can be after preparation completesUnder room temperature, store 180 days and obvious proterties change and hydraulic performance decline do not occur.
Other features and advantages of the present invention are described in detail the detailed description of the invention part subsequently.
Detailed description of the invention
Below the specific embodiment of the present invention is elaborated. Should be understood that, described herein concreteEmbodiment only, for description and interpretation the present invention, is not limited to the present invention.
The invention provides the preparation method of a kind of metal surface chemical pretreatment solution, the method comprises water, silane coupledAgent, water-soluble silicate, promoter, cilicon oxide filler and water-soluble film-forming resin mix successively; Described silane couplerComprise the first silane coupler and the second silane coupler, described the first silane coupler is R-Si (OCH3)3、R-Si(OC2H5)3、R-SiCH3(OCH3)2And R-SiCH3(OC2H5)2In at least one, and R is selected from NH independently of one another2(CH2)2NH(CH2)3-、NH2(CH2)2NHCH2CH(CH3)CH2-、HO(CH2)2NH(CH2)2NH(CH2)3-or NH2(CH2)2NH(CH2)2NH(CH2)3-; Described the second silane coupler is Cl (CH2)3Si(OCH3)3、Cl(CH2)3Si(OC2H5)3、Cl(CH2)3SiCH3(OCH3)2And Cl (CH2)3SiCH3(OC2H5)2In at least one; Described promoter is thiocarbamide and/or urea.
Wherein, at length, the method comprises: (1) mixes water and described silane coupler, obtains uniform liquid A;(2) described uniform liquid A and water-soluble silicate are mixed, obtain uniform liquid B; (3) by described uniform liquid B and shortEnter agent and mix, obtain uniform liquid C; (4) described uniform liquid C and cilicon oxide filler are mixed, obtain even liquidBody D; (5) described uniform liquid D is mixed with water-soluble film-forming resin, obtain uniform liquid E. Wherein, mixThere is no particular limitation for method, as long as can obtain uniform stable phase, preferably makes to mix more even by stirring.
According to the preparation method of metal surface provided by the invention chemical pretreatment solution, wherein, described in 1 weight portionWater-soluble silicate, the consumption of described silane coupler can be 0.5-4.5 weight portion, described the first silane coupler and described inThe weight ratio of the second silane coupler can be 1:0.1-1; Preferably, the consumption of described silane coupler is 1.4-1.8 weightPart, the weight ratio of described the first silane coupler and described the second silane coupler is 1:0.4-0.6.
Wherein, with respect to the described water-soluble silicate of 1 weight portion, the consumption of described promoter can be heavy for 0.2-1.8Amount part, is preferably 0.5-0.7 weight portion.
Wherein, with respect to the described water-soluble silicate of 1 weight portion, the consumption of described cilicon oxide filler can be 0.25-2.2 weight portions, are preferably 0.6-0.85 weight portion.
Wherein, with respect to the described water-soluble silicate of 1 weight portion, in solid, the use of described water-soluble film-forming resinAmount can be 0.8-6.8 weight portion, is preferably 2.1-2.7 weight portion. Herein solid with for calculating or representing consolidating of solid contentBody implication is identical, is water-soluble film-forming resin except remaining composition after desolventizing.
Wherein, with respect to the described water-soluble silicate of 1 weight portion, the consumption of water is 10-100 weight portion, is preferably 25-40 weight portions. It should be noted that, in the present invention, the consumption of said water refers to the amount of the water of other interpolation, do not comprise above-mentioned withIn other component that solution or emulsion mode are added with the amount of water.
According to the preparation method of metal surface provided by the invention chemical pretreatment solution, wherein, under preferable case, described firstSilane coupler is NH2(CH2)2NH(CH2)3Si(OCH3)3、NH2(CH2)2NH(CH2)3Si(OC2H5)3、NH2(CH2)2NH(CH2)3SiCH3(OCH3)2、NH2(CH2)2NHCH2CH(CH3)CH2CH3(OCH3)2、HO(CH2)2NH(CH2)2NH(CH2)3SiCH3(OCH3)2、NH2(CH2)2NH(CH2)2NH(CH2)3SiCH3(OCH3)2And NH2(CH2)2NH(CH2)2NH(CH2)3Si(OCH3)3InAt least one. Wherein, NH2(CH2)2NH(CH2)3Si(OCH3)3(being called N-aminoethyl-γ-aminopropyltrimethoxysilane),NH2(CH2)2NH(CH2)3Si(OC2H5)3(being called N-aminoethyl-gamma-aminopropyl-triethoxy-silane), NH2(CH2)2NH(CH2)3SiCH3(OCH3)2(being called N-aminoethyl-γ-aminopropyl methyl dimethoxysilane), NH2(CH2)2NHCH2CH(CH3)CH2CH3(OCH3)2(being called aminoethyl ammonia isobutyl group methyl dimethoxysilane), HO (CH2)2NH(CH2)2NH(CH2)3SiCH3(OCH3)2(being called 3-(2-ethoxy aminoethyl)-aminopropyl methyl dimethoxysilane), NH2(CH2)2NH(CH2)2NH(CH2)3SiCH3(OCH3)2(being called diethylenetriamine base propyl group methyl dimethoxysilane) and NH2(CH2)2NH(CH2)2NH(CH2)3Si(OCH3)3(being called diethylenetriamine base propyl trimethoxy silicane) can be used as the first silane coupler, and commercially available can be used as is silane coupledCommodity shown in the various above-mentioned chemical formula of agent may be used to the present invention, for example, purchased from the limited public affairs of Hubei moral nation new chemical materialsThe trade mark of department is the commercially available product of DB-792, DB-793, DB-602, DB-604, DB-2602, DB-5551 and DB-4552. Wherein,More preferably described the first silane coupler is NH2(CH2)2NH(CH2)3Si(OCH3)3、NH2(CH2)2NH(CH2)3Si(OC2H5)3WithNH2(CH2)2NH(CH2)3SiCH3(OCH3)2In at least one.
According to the preparation method of metal surface provided by the invention chemical pretreatment solution, wherein, Cl (CH2)3Si(OCH3)3(claimFor γ-r-chloropropyl trimethoxyl silane), Cl (CH2)3Si(OC2H5)3(being called γ-chloropropyl triethoxysilane), Cl (CH2)3SiCH3(OCH3)2(being called gamma-chloropropylmethyldimethoxysilane) and Cl (CH2)3SiCH3(OC2H5)2(be called γ-chlorine thirdYlmethyl diethoxy silane) can be used as the second silane coupler, commercially available various above-mentionedization that can be used as silane couplerCommodity shown in formula may be used to the present invention, for example, be DB-purchased from the trade mark of Debang Chemical New Material Co., Ltd.231, the commercially available product of DB-230, DB-221 and DB-220. Wherein, more preferably described the second silane coupler is Cl (CH2)3Si(OCH3)3(being called γ-r-chloropropyl trimethoxyl silane).
According to the preparation method of metal surface provided by the invention chemical pretreatment solution, wherein, described water-soluble silicate canThink sodium metasilicate and/or potassium silicate. Described sodium metasilicate can be in anhydrous sodium metasilicate, SODIUM METASILICATE PENTAHYDRATE and nine water sodium metasilicate extremelyFew a kind of. And the consumption of described water-soluble silicate is to calculate with the amount of anhydrous silicate.
According to the preparation method of metal surface provided by the invention chemical pretreatment solution, wherein, described cilicon oxide filler does not haveSpecial requirement, can be the various fillers taking silica as main body, and for example, described cilicon oxide filler can be nanometer titanium dioxideSilica flour and/or nano silicon dioxide sol; Under preferable case, the particle diameter of the silica in described cilicon oxide filler can be 5-90nm, more preferably 5-30nm, for example, can use purchased from the trade mark of Asahi Denka Co., Ltd. for AT-30, AT-30S, AT-40,The commercially available product of AT-30A and AT-20, or be the city of SS-25 and SS-30 purchased from the trade mark of Shandong Bai Te new material Co., LtdSell product. For example, and the consumption of cilicon oxide filler is to calculate with the weight of silica itself, the use of nano silicon dioxide solAmount is to calculate with the amount of the silica in colloidal sol, is multiplied by its dioxide-containing silica with the weight of nano silicon dioxide solThe numerical computations obtaining after percentage (weight).
According to the preparation method of metal surface provided by the invention chemical pretreatment solution, wherein, described water-soluble film-forming resinCan be for various water miscible and can be used in modification or the unmodified resin of film forming, described resin can be with suitable systemProduct form is used, for example, in water-soluble emulsion, water-soluble solution and water-soluble solid at least one, and the present invention is not specialRequirement, if the film forming of can be used in, for example, described water-soluble film-forming resin can be water-soluble polyester film-forming resin (By polyalcohols monomer and polynary acids monomer polymerization and water-soluble film-forming resin, for example encourage precious fine chemistry industry purchased from GuangzhouCo., Ltd, the mylar of trade mark CB2200), water-soluble phenylpropyl alcohol film-forming resin is (by styrene monomer and acrylic acid(ester) class monomer polymerization and water-soluble film-forming resin, for example, purchased from Guangzhou Chao Long Chemical Industry Science Co., Ltd, the trade mark isThe benzene emulsion of xy-108b), soluble epoxide film-forming resin (by the monomer polymerization that contains epoxy radicals water-soluble one-tenthFilm resin, for example, purchased from Dongguan City Heima Chemical Co., Ltd., the epoxy resin that the trade mark is BH620), soluble polyurethane film formingResin (by multicomponent isocyanate class monomer and multi-hydroxy compounds monomer polymerization and water-soluble film-forming resin, exampleAs purchased from Jinjiang, Fujian Province Jian Hua company, the polyurethane resin of the trade mark 812), water-soluble silicon the third film-forming resin is (by silicone based listBody and acrylic acid (ester) class monomer polymerization and water-soluble film-forming resin, for example Qingdao paint company TC-05 type silicon third of making the country prosperousEmulsion, solid content is 48 % by weight), the water-soluble acrylic film-forming resin (water being obtained by acrylic acid (ester) class monomer polymerizationDissolubility film-forming resin, the acrylic resin that is for example A-3418 purchased from the trade mark of Guangzhou Ou Peng chemical industry) and water-soluble fluorine carbon film formingResin (water-soluble film-forming resin being obtained by fluorinated monomer polymerization, for example, purchased from Beijing Shouchuang Nano Techn Co., Ltd.,The trade mark is the water-base fluorocarbon emulsion of SKFT-I) at least one; Under preferable case, described water-soluble film-forming resin is water-solublePhenylpropyl alcohol film-forming resin, soluble epoxide film-forming resin, water-soluble silicon the third film-forming resin, water-soluble acrylic film-forming resin, water-solubleAt least one in based polyurethane film-forming resin and water-soluble polyester film-forming resin. More preferably, wherein, described water-soluble silicon thirdFilm-forming resin be Silomer8861 emulsion (purchased from RichdaleSpecialChemicalsInc., auspicious moral special chemical public affairsDepartment).
According to the preparation method of metal surface provided by the invention chemical pretreatment solution, wherein, in order further to improve and to formThe greasy property of protecting film, under preferable case, this preparation method also comprises: the thing after water and silane coupler are mixedMaterial mixes with lubricating auxiliary agent, the water-based emulsion that described lubricating auxiliary agent is dimethicone, polyether-modified polysiloxanes, poly-One or more in the water-based emulsion of ethylene waxes and the water-based emulsion of OPE.
More preferably, with respect to the described water-soluble silicate of 1 weight portion, the content of described lubricating auxiliary agent is 0.2-1.8Weight portion, more preferably 0.5-0.7 weight portion.
Wherein, the solid content of the water-based emulsion of described dimethicone can be 10-90 % by weight, is preferably 30-80 heavyAmount %. It should be noted that, the water-based emulsion of dimethicone is for preparing metal surface provided by the invention chemical pretreatment solutionTime, its consumption refers to that the gross weight of water-based emulsion is multiplied by the numerical value obtaining after its solid content. It should be noted that described dimethylThe solid content of the water-based emulsion of silicone oil refers to the content of the water-based emulsion of the described dimethicone of preparation dimethicone used.Described dimethicone refers to water-insoluble unmodified dimethicone.
Wherein, the dimethyl-silicon oil viscosity in the water-based emulsion of described dimethicone can be 500-50000mPaS, is preferably 1000-40000mPaS, more preferably 1500-30000mPaS.
Wherein, described polyether-modified polysiloxanes is commonly called as water-soluble dimethyl silicone oil, existing various water-soluble diformazansBase silicone oil all can be used for realizing object of the present invention as described lubricating auxiliary agent in the present invention. Preferably described polyether-modifiedPolysiloxanes is that viscosity is 100-10000mPaS, is preferably 500-8000mPaS, more preferably 1000-6000mPaS,Further be preferably the water-soluble dimethyl silicone oil of 2000-5000mPaS.
It should be noted that, do not do in the situation of contrary explanation in the present invention, described viscosity refers to and records at 25 DEG CApparent viscosity numerical value.
Wherein, the water-based emulsion of described Tissuemat E can be by the water obtaining after Tissuemat E emulsification according to conventional methodProperty emulsion, the solid content of the water-based emulsion of described Tissuemat E can be 30-60 % by weight, is preferably 40-50 % by weight. NeedBright, the water-based emulsion of Tissuemat E is when preparing metal surface provided by the invention chemical pretreatment solution, and its consumption isThe gross weight that refers to water-based emulsion is multiplied by the numerical value obtaining after its solid content.
Wherein, the fusing point of the Tissuemat E in the water-based emulsion of described Tissuemat E can be 90-130 DEG C, is preferably100-120 DEG C, more preferably 105-115 DEG C.
Wherein, the water-based emulsion of described OPE can be by after OPE emulsification according to conventional methodThe water-based emulsion obtaining, the solid content of the water-based emulsion of described OPE can be 30-60 % by weight, is preferably 40-50% by weight. It should be noted that, the water-based emulsion of OPE is being located for preparing metal surface provided by the invention chemistryWhen reason liquid, its consumption refers to that the gross weight of water-based emulsion is multiplied by the numerical value obtaining after its solid content.
Wherein, the fusing point of the OPE in the water-based emulsion of described OPE can be 80-120 DEG C,Be preferably 90-115 DEG C, more preferably 100-110 DEG C.
It should be noted that, in the present invention, do not do in the situation of contrary explanation, Tissuemat E and OPE moltenPoint refers to the numerical value of measuring according to mensuration-cooling curve method of GB/T2539-2008 pertroleum wax fusing point.
Wherein, the acid number of the OPE in the water-based emulsion of described OPE can be 5-60mgKOH/G, is preferably 10-50mgKOH/g. Wherein, described acid number is the number of measuring according to GB/T264-83 petroleum product acid value measuring methodValue.
The present invention also provides the metal surface preparing according to preparation method as above chemical pretreatment solution. ItsIn, in preparation method as above, obtain added water-soluble film-forming resin and mix after material (, obtainUniform liquid E) can be used as metal surface of the present invention chemical pretreatment solution and use.
In addition, metal surface of the present invention chemical pretreatment solution can also contain other various chemistry places, metal surface that do not affectThe component of reason fluidity matter, as one or more in dyestuff, pigment, dispersant and defoamer. With this metal surface chemical treatmentThe gross weight of liquid is benchmark, and the content of other component is no more than 20 % by weight, is preferably no more than 10 % by weight. Described defoamer is passableVarious defoamer well known in the art, such as, in polyethers defoamer, higher alcohols defoamer and silicon defoamer etc.Kind or multiple. More particularly, described defoamer can be for being purchased from for example Co., Ltd of the large Creative Science and Technology Co. Ltd of Dongying danSD-401 series defoamer in one or more. Under preferable case, taking the total amount of described metal surface chemical pretreatment solution asBenchmark, the content of described defoamer is 0.01-0.05 % by weight.
Correspondingly, the preparation method of metal surface provided by the invention chemical pretreatment solution can also comprise that to add other variousDo not affect the component of metal surface chemical pretreatment solution character the step mixing. These other various metal surfaces that do not affectThe component of chemical pretreatment solution character can add adding after water-soluble film-forming resin again.
Metal surface of the present invention chemical pretreatment solution can directly use without dilution.
The present invention also provides above-mentioned metal surface chemical pretreatment solution in the purposes of preparing in metal material. Above-mentioned metal watchSurface chemistry treatment fluid can be in the mode of this area routine for the preparation of various metal materials.
According to hot-dip metal plated material provided by the invention, this hot-dip metal plated material comprises galvanizing metal base and is attached toCoating on this hot-dip metal plated base material, described hot-dip metal plated base material is galvanizing metal base, hot-dip aluminizing zinc metal base and heatAt least one in aluminum-zinc alloy magnesium metal base material, described coating is the curing product of metal surface as above chemical pretreatment solutionThing.
Wherein, described galvanizing metal base can be the metal base that contains zinc coating, in described zinc coating, and the containing of zincAmount can be 92.5-95.5 % by weight. Described zinc coating also can contain other conventional ingredient, as silicon.
Wherein, described hot-dip aluminizing zinc metal base can be the metal base that contains zinc-aluminium coating, in described zinc-aluminium coating,The content of zinc can be 41.5-43.5 % by weight, and the content of aluminium can be 51.5-55.0 % by weight. Described zinc-aluminium coating also can containThere is other conventional ingredient, as silicon.
Wherein, hot-dip aluminizing zinc magnesium metal base material can be the metal base that contains aluminium zinc-magnesium coating, described aluminium zinc-magnesium coatingIn, the content of zinc can be 85.5-99.2 % by weight, and the content of aluminium can be 0.2-11 % by weight, and the content of magnesium can be 0.5-3% by weight. Described aluminium zinc-magnesium coating also can contain other conventional ingredient, as silicon.
According to hot-dip metal plated material provided by the invention, wherein, the thickness of described coating can be on hot-dip metal plated base materialThe conventional thickness of erosion shield, in order to improve the performance of described coating, under preferable case, the thickness of described coating is0.05-2 micron can be preferably 0.1-1 micron. Wherein, the thickness of coating XRF(XRF) measuring instrument mensurationNumerical value.
According to hot-dip metal plated material provided by the invention, wherein, on hot-dip metal plated base material, adhere to the method for described coatingCan comprise described metal surface chemical pretreatment solution is attached on the surface of hot-dip metal plated base material, then dry, dry temperatureDegree can be 60-120 DEG C, is preferably 90-110 DEG C, and the time can be 0.5-3 second. The use of described metal surface chemical pretreatment solutionAmount can be determined according to the thickness of coating.
Wherein, described dry method, can be a kind of or many in heated-air drying, eddy-current heating and infrared radiation heatingKind.
In the present invention, do not do in the situation of contrary explanation, the volume of all liq and solid all refers to 20 DEG C, 1 normal atmosphereThe volume of depressing.
Below will be explained in further detail the present invention by embodiment.
Embodiment 1
By the silane coupler of the water of 28 weight portions and 1.6 weight portions (by the first silane coupler and second silane coupledAgent composition) under the mixing speed of 1500 revs/min, be mixed to evenly, obtain uniform liquid A, wherein, the first silane couplerFor NH2(CH2)2NH(CH2)3Si(OCH3)3, purchased from Debang Chemical New Material Co., Ltd., trade mark DB-792, the second silaneCoupling agent is Cl (CH2)3Si(OCH3)3, purchased from Debang Chemical New Material Co., Ltd., trade mark DB-231, the first silane is evenThe weight ratio of connection agent and the second silane coupler is 1:0.5.
By the water-soluble silicate of whole uniform liquid A and 1 weight portion, (metasilicate pentahydrate sodium, purchased from Qingdao great RunizationWork Co., Ltd) under the mixing speed of 1500 revs/min, be mixed to evenly, obtain uniform liquid B.
The promoter (thiocarbamide) of whole uniform liquid B and 0.6 weight portion is mixed under the mixing speed of 1500 revs/minBe bonded to evenly, obtain uniform liquid C.
By the cilicon oxide filler of whole uniform liquid C and 0.72 weight portion, (nano silicon dioxide sol, purchased from Shandong hundredSpy's new material Co., Ltd, the trade mark is SS-30, weight is in silica) under the mixing speed of 1500 revs/min, be mixed toEvenly, obtain uniform liquid D.
By water-soluble film-forming resin (water-soluble silicon third film forming of whole uniform liquid D and 2.4 weight portions (in solid)Resin (Silomer8861 emulsion (purchased from RichdaleSpecialChemicalsInc., Rui De special chemical company, GuContent is 43 % by weight))) under the mixing speed of 1500 revs/min, be mixed to evenly, obtain uniform liquid E. Uniform liquid EBe the metal surface chemical pretreatment solution of the present embodiment.
Comparative example 1
Prepare metal surface chemical pretreatment solution according to the method for embodiment 1, different, first in mixing container usedAdd water, silane coupler, water-soluble silicate, promoter, cilicon oxide filler and water-soluble film-forming resin simultaneously, then 1500Rev/min mixing speed under be mixed to evenly, obtain the metal surface chemical pretreatment solution of this comparative example.
Comparative example 2
Prepare metal surface chemical pretreatment solution according to the method for embodiment 1, different, by water, water-soluble film-forming resin,Water-soluble silicate, promoter, cilicon oxide filler and silane coupler mix successively, obtain the metal surface of this comparative exampleChemical pretreatment solution. , the application of sample order of silane coupler and water-soluble film-forming resin is exchanged.
Comparative example 3
Prepare metal surface chemical pretreatment solution according to the method for embodiment 1, different, by water, silane coupler, oxidationSilicon filler, promoter, water-soluble silicate and water-soluble film-forming resin mix successively, obtain the metal surface of this comparative exampleChemical pretreatment solution. , the application of sample order of water-soluble silicate and cilicon oxide filler is exchanged.
Comparative example 4
Prepare metal surface chemical pretreatment solution according to the method for embodiment 1, different, 1.6 weight portions silane coupledAgent is all the first silane coupler, does not contain the second silane coupler.
Comparative example 5
Prepare metal surface chemical pretreatment solution according to the method for embodiment 1, different, 1.6 weight portions silane coupledAgent is all the second silane coupler, does not contain the first silane coupler.
Embodiment 2
By the silane coupler of the water of 25 weight portions and 1.4 weight portions (by the first silane coupler and second silane coupledAgent composition) under the mixing speed of 1500 revs/min, be mixed to evenly, obtain uniform liquid A, wherein, the first silane couplerFor NH2(CH2)2NH(CH2)3Si(OC2H5)3, purchased from Debang Chemical New Material Co., Ltd., trade mark DB-793, the second silaneCoupling agent is Cl (CH2)3Si(OCH3)3, purchased from Debang Chemical New Material Co., Ltd., trade mark DB-231, the first silane is evenThe weight ratio of connection agent and the second silane coupler is 1:0.4.
By the water-soluble silicate of whole uniform liquid A and 1 weight portion, (potassium silicate, purchased from Baoding, profit Feng Shiye is limitedCompany) under the mixing speed of 1500 revs/min, be mixed to evenly, obtain uniform liquid B.
By the promoter of whole uniform liquid B and 0.5 weight portion (thiocarbamide and urea etc. weight mixture) 1500Rev/min mixing speed under be mixed to evenly, obtain uniform liquid C.
By the cilicon oxide filler of whole uniform liquid C and 0.6 weight portion, (nano silicon dioxide sol, purchased from the meeting of strain formulaThe ADEKA of society, the trade mark is AT-30, weight is in silica) under the mixing speed of 1500 revs/min, be mixed to evenly, obtainUniform liquid D.
By water-soluble film-forming resin (water-soluble silicon third film forming of whole uniform liquid D and 2.1 weight portions (in solid)Resin (Silomer8861 emulsion (purchased from RichdaleSpecialChemicalsInc., Rui De special chemical company, GuContent is 43 % by weight))) under the mixing speed of 1500 revs/min, be mixed to evenly, obtain uniform liquid E. Uniform liquid EBe the metal surface chemical pretreatment solution of the present embodiment.
Embodiment 3
By the silane coupler of the water of 40 weight portions and 1.8 weight portions (by the first silane coupler and second silane coupledAgent composition) under the mixing speed of 1500 revs/min, be mixed to evenly, obtain uniform liquid A, wherein, the first silane couplerFor NH2(CH2)2NH(CH2)3SiCH3(OCH3)2, purchased from Debang Chemical New Material Co., Ltd., trade mark DB-602, the second siliconAlkane coupling agent is Cl (CH2)3Si(OCH3)3, purchased from Debang Chemical New Material Co., Ltd., trade mark DB-231, the first silaneThe weight ratio of coupling agent and the second silane coupler is 1:0.6.
By the water-soluble silicate of whole uniform liquid A and 1 weight portion, (metasilicate pentahydrate sodium, purchased from Qingdao great RunizationWork Co., Ltd) under the mixing speed of 1500 revs/min, be mixed to evenly, obtain uniform liquid B.
The promoter (urea) of whole uniform liquid B and 0.7 weight portion is mixed under the mixing speed of 1500 revs/minBe bonded to evenly, obtain uniform liquid C.
By the cilicon oxide filler of whole uniform liquid C and 0.85 weight portion, (nano silicon dioxide sol, purchased from the meeting of strain formulaThe ADEKA of society, the trade mark is AT-30, weight is in silica) under the mixing speed of 1500 revs/min, be mixed to evenly, obtainUniform liquid D.
By water-soluble film-forming resin (water-soluble silicon third film forming of whole uniform liquid D and 2.7 weight portions (in solid)Resin (Silomer8861 emulsion (purchased from RichdaleSpecialChemicalsInc., Rui De special chemical company, GuContent is 43 % by weight))) under the mixing speed of 1500 revs/min, be mixed to evenly, obtain uniform liquid E. Uniform liquid EBe the metal surface chemical pretreatment solution of the present embodiment.
Embodiment 4
By the silane coupler of the water of 90 weight portions and 0.6 weight portion (by the first silane coupler and second silane coupledAgent composition) under the mixing speed of 1500 revs/min, be mixed to evenly, obtain uniform liquid A, wherein, the first silane couplerFor NH2(CH2)2NH(CH2)3Si(OCH3)3, purchased from Debang Chemical New Material Co., Ltd., trade mark DB-792, the second silaneCoupling agent is Cl (CH2)3Si(OCH3)3, purchased from Debang Chemical New Material Co., Ltd., trade mark DB-231, the first silane is evenThe weight ratio of connection agent and the second silane coupler is 1:0.4.
By the water-soluble silicate of whole uniform liquid A and 1 weight portion, (metasilicate pentahydrate sodium, purchased from Qingdao great RunizationWork Co., Ltd) under the mixing speed of 1500 revs/min, be mixed to evenly, obtain uniform liquid B.
The promoter (thiocarbamide) of whole uniform liquid B and 0.3 weight portion is mixed under the mixing speed of 1500 revs/minBe bonded to evenly, obtain uniform liquid C.
By the cilicon oxide filler of whole uniform liquid C and 2.1 weight portions, (nano silicon dioxide sol, purchased from Shandong hundredSpy's new material Co., Ltd, the trade mark is SS-30, weight is in silica) under the mixing speed of 1500 revs/min, be mixed toEvenly, obtain uniform liquid D.
By water-soluble film-forming resin (water-soluble silicon third film forming of whole uniform liquid D and 6.5 weight portions (in solid)Resin (Silomer8861 emulsion (purchased from RichdaleSpecialChemicalsInc., Rui De special chemical company, GuContent is 43 % by weight))) under the mixing speed of 1500 revs/min, be mixed to evenly, obtain uniform liquid E. Uniform liquid EBe the metal surface chemical pretreatment solution of the present embodiment.
Embodiment 5
By the silane coupler of the water of 15 weight portions and 4.5 weight portions (by the first silane coupler and second silane coupledAgent composition) under the mixing speed of 1500 revs/min, be mixed to evenly, obtain uniform liquid A, wherein, the first silane couplerFor NH2(CH2)2NH(CH2)3Si(OCH3)3, purchased from Debang Chemical New Material Co., Ltd., trade mark DB-792, the second silaneCoupling agent is Cl (CH2)3Si(OCH3)3, purchased from Debang Chemical New Material Co., Ltd., trade mark DB-231, the first silane is evenThe weight ratio of connection agent and the second silane coupler is 1:0.6.
By the water-soluble silicate of whole uniform liquid A and 1 weight portion, (metasilicate pentahydrate sodium, purchased from Qingdao great RunizationWork Co., Ltd) under the mixing speed of 1500 revs/min, be mixed to evenly, obtain uniform liquid B.
The promoter (thiocarbamide) of whole uniform liquid B and 1.7 weight portions is mixed under the mixing speed of 1500 revs/minBe bonded to evenly, obtain uniform liquid C.
By the cilicon oxide filler of whole uniform liquid C and 0.3 weight portion, (nano silicon dioxide sol, purchased from Shandong hundredSpy's new material Co., Ltd, the trade mark is SS-30, weight is in silica) under the mixing speed of 1500 revs/min, be mixed toEvenly, obtain uniform liquid D.
By water-soluble film-forming resin (water-soluble silicon third film forming of whole uniform liquid D and 1.0 weight portions (in solid)Resin (Silomer8861 emulsion (purchased from RichdaleSpecialChemicalsInc., Rui De special chemical company, GuContent is 43 % by weight))) under the mixing speed of 1500 revs/min, be mixed to evenly, obtain uniform liquid E. Uniform liquid EBe the metal surface chemical pretreatment solution of the present embodiment.
Embodiment 6
Prepare metal surface chemical pretreatment solution according to the method for embodiment 1, different, the first silane coupler is NH2(CH2)2NHCH2CH(CH3)CH2CH3(OCH3)2(purchased from Debang Chemical New Material Co., Ltd., trade mark DB-604).
Embodiment 7
Prepare metal surface chemical pretreatment solution according to the method for embodiment 1, different, the first silane coupler is HO(CH2)2NH(CH2)2NH(CH2)3SiCH3(OCH3)2(purchased from Debang Chemical New Material Co., Ltd., trade mark DB-2602).
Embodiment 8
Prepare metal surface chemical pretreatment solution according to the method for embodiment 1, different, the first silane coupler is NH2(CH2)2NH(CH2)2NH(CH2)3SiCH3(OCH3)2(purchased from Debang Chemical New Material Co., Ltd., trade mark DB-5551).
Embodiment 9
Prepare metal surface chemical pretreatment solution according to the method for embodiment 1, different, the second silane coupler is Cl(CH2)3Si(OC2H5)3(purchased from Debang Chemical New Material Co., Ltd., trade mark DB-230).
Embodiment 10
Prepare metal surface chemical pretreatment solution according to the method for embodiment 1, different, the second silane coupler is Cl(CH2)3SiCH3(OCH3)2(purchased from Debang Chemical New Material Co., Ltd., trade mark DB-221).
Embodiment 11
Prepare metal surface chemical pretreatment solution according to the method for embodiment 1, different, the second silane coupler is Cl(CH2)3SiCH3(OC2H5)2(purchased from Debang Chemical New Material Co., Ltd., trade mark DB-220).
Embodiment 12
Prepare metal surface chemical pretreatment solution according to the method for embodiment 1, different, the first silane coupler and secondThe weight ratio of silane coupler is 1:0.1.
Embodiment 13
Prepare metal surface chemical pretreatment solution according to the method for embodiment 1, different, the first silane coupler and secondThe weight ratio of silane coupler is 1:1.
Embodiment 14
Prepare metal surface chemical pretreatment solution according to the method for embodiment 1, different, use water-soluble silicon the third film forming treeFat (Qingdao make the country prosperous paint company TC-05 type Silicone acrylic emulsion, solid content is 48 % by weight) is as water-soluble film-forming resin, andIn material after water and silane coupler are mixed, add the lubricating auxiliary agent (water-based emulsion of dimethicone and polyether-modifiedPolysiloxanes by weight 1; 1 obtains after mixing, and the water-based emulsion of dimethicone is purchased from Nanjing Hua Tuo Chemical Co., Ltd.,The trade mark is HTR-1, and solid content is 30 % by weight, is the dimethicone emulsification that is 25000mPaS by the apparent viscosity at 25 DEG CAfter obtain; Polyether-modified polysiloxanes is purchased from dyeing and finishing auxiliaries for textile Co., Ltd., Factory of Dongguan Acer, apparent sticky at 25 DEG CDegree is 3000mPaS) and mix, wherein, with respect to the water-soluble silicate of 1 weight portion, the consumption of lubricating auxiliary agent is0.6 weight portion.
Embodiment 15
Prepare metal surface chemical pretreatment solution according to the method for embodiment 14, different, do not add lubricating auxiliary agent.
Embodiment 16
Prepare metal surface chemical pretreatment solution according to the method for embodiment 1, different, use water-soluble phenylpropyl alcohol film forming treeFat (purchased from Guangzhou Chao Long Chemical Industry Science Co., Ltd, the benzene emulsion that the trade mark is xy-108b) is as water-soluble film-forming resin,And add lubricating auxiliary agent (water-based emulsion of Tissuemat E and oxidation in the material after water and silane coupler are mixedThe water-based emulsion of Tissuemat E obtains after 1:1 mixes, and the water-based emulsion of Tissuemat E is purchased from the grand wide plastic cement of Dongguan CityRaw material business department, solid content is 48 % by weight, the fusing point of Tissuemat E is 110-115 DEG C; The water-based emulsion of OPE is purchasedFrom Beijing Zhong Guan special wax Co., Ltd, solid content is 48 % by weight, and the fusing point of OPE is 105-110 DEG C, and acid number is14-21mgKOH/g) and mix, wherein, with respect to the water-soluble silicate of 1 weight portion, the consumption of lubricating auxiliary agent is 0.5Weight portion.
Embodiment 17
Prepare metal surface chemical pretreatment solution according to the method for embodiment 1, different, use soluble epoxide film forming treeFat (purchased from Dongguan City Heima Chemical Co., Ltd., the aqueous epoxy resin emulsion that the trade mark is BH620) is set as water-soluble, film-formingFat, and in material after water and silane coupler are mixed, add lubricating auxiliary agent (water-based emulsion of dimethicone,Purchased from Guangzhou Si Luoke Chemical Co., Ltd., solid content is 80 % by weight, is to be 1500mPaS by the apparent viscosity at 25 DEG CDimethicone emulsification after obtain) and mix, wherein, with respect to the water-soluble silicate of 1 weight portion, lubricating auxiliary agentConsumption be 0.7 weight portion.
Embodiment 18
Prepare metal surface chemical pretreatment solution according to the method for embodiment 1, different, use water-soluble polyester film forming treeFat (purchased from Yancheng, Jiangsu Province Ju Ke Chemical Co., Ltd., the waterborne polyester that the trade mark is PE-10030-P) is set as water-soluble, film-formingFat, and in material after water and silane coupler are mixed, add lubricating auxiliary agent (water-based emulsion of dimethicone,Purchased from Guangzhou Si Luoke Chemical Co., Ltd., solid content is 80 % by weight, is to be 1500mPaS by the apparent viscosity at 25 DEG CDimethicone emulsification after obtain) and mix, wherein, with respect to the water-soluble silicate of 1 weight portion, lubricating auxiliary agentConsumption be 0.7 weight portion.
Preparation Example 1
Getting metal surface chemical pretreatment solution that embodiment 1-18 and comparative example 1-5 obtain is coated on respectively galvanized steel plain sheet and (purchasesFrom Pangang Group Panzhihua Steel Vanadium Co., Ltd., model DX54D, in zinc coat containing zinc 95 % by weight) surface, at 90-110 DEG CHeated-air drying 2 seconds, obtains respectively galvanized steel plain sheet after treatment. Wherein, coating amount makes the coating on galvanized steel plain sheet after treatmentThickness be 0.8 micron. The thickness of coating is to use XRF(XRF) measuring instrument measure numerical value. Wherein, this preparation is realExecuting the metal surface chemical pretreatment solution using in example is all to have stored the metal of 1 day after having prepared (obtaining uniform liquid E)Chemical surface treatment liquid.
Preparation Example 2-4
Prepare galvanized steel plain sheet after treatment according to the method for Preparation Example 1, different, the metal surface chemistry of useTreatment fluid is all to have stored the metal surface chemical pretreatment solution of 60,120 and 180 days after having prepared (obtaining uniform liquid E).
Test implementation example 1
By the requirement specifying in GB/T101251997, carry out neutral salt spray test, measure respectively Preparation Example 1-4'sThe corrosion resisting property of galvanized steel plain sheet after treatment. It is qualified to be considered as by " salt spray test 168h, corrosion area < 3% ".
On M-2000 ring block type friction and wear tester, measure according to its description the processing that Preparation Example 1 obtainsAfter the coefficient of kinetic friction of coating of galvanized steel plain sheet.
Test result as above is as shown in table 1. Number of days in bracket represents the storage of metal surface chemical pretreatment solutionTime.
Visible according to the data of table 1, the corrosion resistance of the protecting film that metal surface provided by the invention chemical pretreatment solution formsVery good, and the storage endurance of metal surface provided by the invention chemical pretreatment solution is also very good. And, according to table 1Data visible, at the preferred described water-soluble silicate with respect to 1 weight portion, the content of described promoter is that 0.5-0.7 is heavyAmount part, the consumption of described silane coupler is 1.4-1.8 weight portion, the first silane coupler and described the second silane couplerWeight ratio is 1:0.4-6, and the consumption of described cilicon oxide filler is 0.6-0.85 weight portion, in solid, and described water-soluble, film-formingThe consumption of resin is 2.1-2.7 weight portion, and the consumption of water is in the situation of 25-40 weight portion, can further improve described goldThe corrosion resistance of the protecting film that metal surface chemical pretreatment solution forms. And, visible according to the data of table 1, preferably described water-solubleSilicon the third film-forming resin is in the situation of Silomer8861 emulsion, or preferred described raw mixture also contains the feelings of lubricating auxiliary agentUnder condition, can further improve the lubricity of the protecting film of described metal surface chemical pretreatment solution formation. In addition, according to table 1Data are NH at preferred described the first silane coupler2(CH2)2NH(CH2)3Si(OCH3)3、NH2(CH2)2NH(CH2)3Si(OC2H5)3And NH2(CH2)2NH(CH2)3SiCH3(OCH3)2In at least one, preferably described the second silane coupler is Cl(CH2)3Si(OCH3)3Situation under, can further improve the anti-corrosion of protecting film that described metal surface chemical pretreatment solution formsProperty.
Table 1
More than describe the preferred embodiment of the present invention in detail, still, the present invention is not limited in above-mentioned embodimentDetail, within the scope of technical conceive of the present invention, can carry out multiple simple variant to technical scheme of the present invention, thisA little simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characterictic described in above-mentioned detailed description of the invention, at lance notIn the situation of shield, can combine by any suitable mode, for fear of unnecessary repetition, the present invention to various canThe combination explanation no longer separately of energy.
In addition, between various embodiment of the present invention, also can be combined, as long as it is without prejudice to thisThe thought of invention, it should be considered as content disclosed in this invention equally.
Claims (11)
1. a preparation method for metal surface chemical pretreatment solution, the method comprises water, silane coupler, water-soluble silicic acidSalt, promoter, cilicon oxide filler and water-soluble film-forming resin mix successively; Described silane coupler comprises that the first silane is evenConnection agent and the second silane coupler, described the first silane coupler is R-Si (OCH3)3、R-Si(OC2H5)3、R-SiCH3(OCH3)2And R-SiCH3(OC2H5)2In at least one, and R is selected from NH independently of one another2(CH2)2NH(CH2)3-、NH2(CH2)2NHCH2CH(CH3)CH2-、HO(CH2)2NH(CH2)2NH(CH2)3-or NH2(CH2)2NH(CH2)2NH(CH2)3-; Described the second siliconAlkane coupling agent is Cl (CH2)3Si(OCH3)3、Cl(CH2)3Si(OC2H5)3、Cl(CH2)3SiCH3(OCH3)2And Cl (CH2)3SiCH3(OC2H5)2In at least one; Described promoter is thiocarbamide and/or urea; Wherein, described water-soluble with respect to 1 weight portionSilicate, the consumption of described promoter is 0.2-1.8 weight portion, the consumption of described silane coupler is 0.5-4.5 weight portion, instituteThe weight ratio of stating the first silane coupler and described the second silane coupler is 1:0.1-1, and the consumption of described cilicon oxide filler is0.25-2.2 weight portion, in solid, the consumption of described water-soluble film-forming resin is 0.8-6.8 weight portion, the consumption of water is 10-100 weight portions.
2. preparation method according to claim 1, wherein, with respect to the described water-soluble silicate of 1 weight portion, described shortThe consumption that enters agent is 0.5-0.7 weight portion, and the consumption of described silane coupler is 1.4-1.8 weight portion, and described the first silane is evenThe weight ratio of connection agent and described the second silane coupler is 1:0.4-0.6, and the consumption of described cilicon oxide filler is that 0.6-0.85 is heavyAmount part, in solid, the consumption of described water-soluble film-forming resin is 2.1-2.7 weight portion, the consumption of water is 25-40 weight portion.
3. preparation method according to claim 1 and 2, wherein, described the first silane coupler is NH2(CH2)2NH(CH2)3Si(OCH3)3、NH2(CH2)2NH(CH2)3Si(OC2H5)3、NH2(CH2)2NH(CH2)3SiCH3(OCH3)2、NH2(CH2)2NHCH2CH(CH3)CH2SiCH3(OCH3)2、HO(CH2)2NH(CH2)2NH(CH2)3SiCH3(OCH3)2、NH2(CH2)2NH(CH2)2NH(CH2)3SiCH3(OCH3)2And NH2(CH2)2NH(CH2)2NH(CH2)3Si(OCH3)3In at least one.
4. preparation method according to claim 1 and 2, wherein, described the second silane coupler is Cl (CH2)3Si(OCH3)3。
5. preparation method according to claim 1 and 2, wherein, described water-soluble film-forming resin is water-soluble polyester film formingThe third one-tenth of resin, water-soluble phenylpropyl alcohol film-forming resin, soluble epoxide film-forming resin, soluble polyurethane film-forming resin, water-soluble siliconAt least one in film resin, water-soluble acrylic film-forming resin and water-soluble fluorine carbon film-forming resin.
6. preparation method according to claim 5, wherein, described water-soluble silicon the third film-forming resin is Silomer8861 breastLiquid.
7. preparation method according to claim 1 and 2, wherein, this preparation method also comprises: by mixed to water and silane couplerMaterial after closing evenly mixes with lubricating auxiliary agent, water-based emulsion that described lubricating auxiliary agent is dimethicone, polyether-modifiedPolysiloxanes, the water-based emulsion of Tissuemat E and the water-based emulsion of OPE in one or more, with respect to 1 weightThe described water-soluble silicate of amount part, the consumption of described lubricating auxiliary agent is 0.2-1.8 weight portion.
8. the metal surface chemical pretreatment solution that in claim 1-7, the preparation method described in any one prepares.
9. metal surface claimed in claim 8 chemical pretreatment solution is in the purposes of preparing in metal material.
10. a hot-dip metal plated material, this hot-dip metal plated material comprises hot-dip metal plated base material and is attached to this hot-dip metal plated base materialOn coating, described hot-dip metal plated base material is galvanizing metal base, hot-dip aluminizing zinc metal base and hot-dip aluminizing zinc magnesium metal baseAt least one in material, is characterized in that, described coating is the curing product of metal surface claimed in claim 8 chemical pretreatment solutionThing.
11. hot-dip metal plated materials according to claim 10, wherein, the thickness of described coating is 0.1-1 micron.
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| CN101535529A (en) * | 2006-12-13 | 2009-09-16 | 杰富意钢铁株式会社 | Surface-treated zinc-coated steel sheet excellent in planar -part corrosion resistance, blackening resistance, and appearance and corrosion resistance after press forming |
| WO2011122119A1 (en) * | 2010-03-29 | 2011-10-06 | 関西ペイント株式会社 | Surface-treating composition |
| CN102257178A (en) * | 2008-12-16 | 2011-11-23 | 日本帕卡濑精株式会社 | Surface treating agent for metallic materials |
| CN103031043A (en) * | 2011-09-28 | 2013-04-10 | 攀钢集团攀枝花钢铁研究院有限公司 | Metal protective coating and hot galvanizing metal material and hot dip aluminum-zinc metal material |
| CN103031042A (en) * | 2011-09-28 | 2013-04-10 | 攀钢集团攀枝花钢铁研究院有限公司 | Metal protective coating and hot galvanizing metal material and hot dip aluminum-zinc metal material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101535529A (en) * | 2006-12-13 | 2009-09-16 | 杰富意钢铁株式会社 | Surface-treated zinc-coated steel sheet excellent in planar -part corrosion resistance, blackening resistance, and appearance and corrosion resistance after press forming |
| CN102257178A (en) * | 2008-12-16 | 2011-11-23 | 日本帕卡濑精株式会社 | Surface treating agent for metallic materials |
| WO2011122119A1 (en) * | 2010-03-29 | 2011-10-06 | 関西ペイント株式会社 | Surface-treating composition |
| CN103031043A (en) * | 2011-09-28 | 2013-04-10 | 攀钢集团攀枝花钢铁研究院有限公司 | Metal protective coating and hot galvanizing metal material and hot dip aluminum-zinc metal material |
| CN103031042A (en) * | 2011-09-28 | 2013-04-10 | 攀钢集团攀枝花钢铁研究院有限公司 | Metal protective coating and hot galvanizing metal material and hot dip aluminum-zinc metal material |
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