CN104059489A - Metal surface chemical treatment liquid and preparation method and use thereof, and hot-dip plated metal material - Google Patents
Metal surface chemical treatment liquid and preparation method and use thereof, and hot-dip plated metal material Download PDFInfo
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- CN104059489A CN104059489A CN201310160763.8A CN201310160763A CN104059489A CN 104059489 A CN104059489 A CN 104059489A CN 201310160763 A CN201310160763 A CN 201310160763A CN 104059489 A CN104059489 A CN 104059489A
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Abstract
The invention provides a preparation method of a metal surface chemical treatment liquid. The method comprises successively mixing evenly water, silane coupling agents, water-soluble silicate, an accelerant, a silica filler and water-soluble film-forming resin. The invention also provides the metal surface chemical treatment liquid prepared according to the preparation method and a use thereof in preparation of metal materials. The invention further provides a hot-dip plated metal material which comprises a hot-dip plated metal substrate and a coating layer adhering onto the hot-dip plated metal substrate, wherein the coating layer is a cured product of the metal surface chemical treatment liquid. A protective film formed by the metal surface chemical treatment liquid provided by the invention is quite excellent in corrosion resistance. In addition, the metal surface chemical treatment liquid provided by the invention is quite excellent in storage resistance, and can be stored for 180 days at room temperature after completion of preparation but does not generate obvious character changes and performance reduction.
Description
Technical field
The present invention relates to metal protection field, particularly, relate to purposes and the hot-dip metal plated material of the preparation method of a kind of metallic surface chemical pretreatment solution, the metallic surface chemical pretreatment solution being obtained by this preparation method, this metallic surface chemical pretreatment solution.
Background technology
Hot-dip metal plated material, comprises hot-dip galvanized metal material and hot-dip aluminizing zinc metallic substance, in order to prevent corrosion, and all can be at the surface of hot-dip metal plated material coating layer of metal chemical conversion treatment liquid to form protective film.Thereby the performance of metallic surface chemical pretreatment solution is very important for the rust protection of hot-dip metal plated material.
For example, CN101608306A discloses a kind of passivating solution, also belong to a kind of metallic surface chemical pretreatment solution, it is characterized in that, this passivating solution is the aqueous solution that contains water-soluble molybdenum compound, boric acid, water soluble organic substance and silicon sol, wherein, described water soluble organic substance is the mixture of alcohol and organic carboxyl acid.
But the solidity to corrosion that experiment showed, the protective film that this metallic surface chemical pretreatment solution forms is still poor.
Summary of the invention
The poor defect of solidity to corrosion that the object of the invention is to overcome the protective film that existing metallic surface chemical pretreatment solution forms, provides a kind of metallic surface chemical pretreatment solution that can form the good protective film of solidity to corrosion.
To achieve these goals, the invention provides the preparation method of a kind of metallic surface chemical pretreatment solution, the method comprises water, silane coupling agent, water-soluble silicate, promotor, cilicon oxide filler and water-soluble film-forming resin is mixed successively; Described silane coupling agent comprises the first silane coupling agent and the second silane coupling agent, and described the first silane coupling agent is R-Si (OCH
3)
3, R-Si (OC
2h
5)
3, R-SiCH
3(OCH
3)
2and R-SiCH
3(OC
2h
5)
2in at least one, and R is selected from NH independently of one another
2(CH
2)
2nH (CH
2)
3-, NH
2(CH
2)
2nHCH
2cH (CH
3) CH
2-, HO (CH
2)
2nH (CH
2)
2nH (CH
2)
3-or NH
2(CH
2)
2nH (CH
2)
2nH (CH
2)
3-; Described the second silane coupling agent is Cl (CH
2)
3si (OCH
3)
3, Cl (CH
2)
3si (OC
2h
5)
3, Cl (CH
2)
3siCH
3(OCH
3)
2and Cl (CH
2)
3siCH
3(OC
2h
5)
2in at least one; Described promotor is thiocarbamide and/or urea.
The present invention also provides the metallic surface preparing according to preparation method as above chemical pretreatment solution.
The present invention also provides the purposes of above-mentioned metallic surface chemical pretreatment solution in preparing metallic substance.
The present invention also provides a kind of hot-dip metal plated material, this hot-dip metal plated material comprises hot-dip metal plated base material and is attached to the coating on this hot-dip metal plated base material, described hot-dip metal plated base material is at least one in pot galvanize metal base, hot-dip aluminizing zinc metal base and hot-dip aluminizing zinc magnesium metal base material, it is characterized in that, described coating is the cured product of metallic surface as above chemical pretreatment solution.
By technique scheme, the solidity to corrosion of the protective film that metallic surface provided by the invention chemical pretreatment solution forms is very good.In addition, the storage endurance of metallic 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 degradation after preparation completes.
Other features and advantages of the present invention partly in detail are described the embodiment subsequently.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein 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 metallic surface chemical pretreatment solution, the method comprises water, silane coupling agent, water-soluble silicate, promotor, cilicon oxide filler and water-soluble film-forming resin is mixed successively; Described silane coupling agent comprises the first silane coupling agent and the second silane coupling agent, and described the first silane coupling agent is R-Si (OCH
3)
3, R-Si (OC
2h
5)
3, R-SiCH
3(OCH
3)
2and R-SiCH
3(OC
2h
5)
2in at least one, and R is selected from NH independently of one another
2(CH
2)
2nH (CH
2)
3-, NH
2(CH
2)
2nHCH
2cH (CH
3) CH
2-, HO (CH
2)
2nH (CH
2)
2nH (CH
2)
3-or NH
2(CH
2)
2nH (CH
2)
2nH (CH
2)
3-; Described the second silane coupling agent is Cl (CH
2)
3si (OCH
3)
3, Cl (CH
2)
3si (OC
2h
5)
3, Cl (CH
2)
3siCH
3(OCH
3)
2and Cl (CH
2)
3siCH
3(OC
2h
5)
2in at least one; Described promotor is thiocarbamide and/or urea.
Wherein, at length, the method comprises: (1) mixes water and described silane coupling agent, obtains uniform liquid A; (2) described uniform liquid A and water-soluble silicate are mixed, obtain uniform liquid B; (3) described uniform liquid B and promotor are mixed, obtain uniform liquid C; (4) described uniform liquid C and cilicon oxide filler are mixed, obtain uniform liquid D; (5) described uniform liquid D is mixed with water-soluble film-forming resin, obtain uniform liquid E.Wherein, there is no particular limitation for the method mixing, as long as can obtain uniform stable phase, preferably by stirring, makes to mix more even.
According to the preparation method of metallic surface provided by the invention chemical pretreatment solution, wherein, described water-soluble silicate with respect to 1 weight part, the consumption of described silane coupling agent can be 0.5-4.5 weight part, and the weight ratio of described the first silane coupling agent and described the second silane coupling agent can be 1:0.1-1; Preferably, the consumption of described silane coupling agent is 1.4-1.8 weight part, and the weight ratio of described the first silane coupling agent and described the second silane coupling agent is 1:0.4-0.6.
Wherein, with respect to the described water-soluble silicate of 1 weight part, the consumption of described promotor can be 0.2-1.8 weight part, is preferably 0.5-0.7 weight part.
Wherein, with respect to the described water-soluble silicate of 1 weight part, the consumption of described cilicon oxide filler can be 0.25-2.2 weight part, is preferably 0.6-0.85 weight part.
Wherein, with respect to the described water-soluble silicate of 1 weight part, in solid, the consumption of described water-soluble film-forming resin can be 0.8-6.8 weight part, is preferably 2.1-2.7 weight part.Herein solid with for calculating or representing that the solid implication of solid content is identical, be water-soluble film-forming resin except remaining composition after desolventizing.
Wherein, with respect to the described water-soluble silicate of 1 weight part, the consumption of water is 10-100 weight part, is preferably 25-40 weight part.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 in above-mentioned other component of adding with solution or emulsion mode with the amount of water.
According to the preparation method of metallic surface provided by the invention chemical pretreatment solution, wherein, under preferable case, described the first silane coupling agent is NH
2(CH
2)
2nH (CH
2)
3si (OCH
3)
3, NH
2(CH
2)
2nH (CH
2)
3si (OC
2h
5)
3, NH
2(CH
2)
2nH (CH
2)
3siCH
3(OCH
3)
2, NH
2(CH
2)
2nHCH
2cH (CH
3) CH
2cH
3(OCH
3)
2, HO (CH
2)
2nH (CH
2)
2nH (CH
2)
3siCH
3(OCH
3)
2, NH
2(CH
2)
2nH (CH
2)
2nH (CH
2)
3siCH
3(OCH
3)
2and NH
2(CH
2)
2nH (CH
2)
2nH (CH
2)
3si (OCH
3)
3in at least one.Wherein, NH
2(CH
2)
2nH (CH
2)
3si (OCH
3)
3(being called N-aminoethyl-γ-aminopropyltrimethoxysilane), NH
2(CH
2)
2nH (CH
2)
3si (OC
2h
5)
3(being called N-aminoethyl-γ-aminopropyl triethoxysilane), NH
2(CH
2)
2nH (CH
2)
3siCH
3(OCH
3)
2(being called N-aminoethyl-γ-aminopropyl methyl dimethoxysilane), NH
2(CH
2)
2nHCH
2cH (CH
3) CH
2cH
3(OCH
3)
2(being called aminoethyl ammonia isobutyl-methyl dimethoxysilane), HO (CH
2)
2nH (CH
2)
2nH (CH
2)
3siCH
3(OCH
3)
2(being called 3-(2-hydroxyethyl aminoethyl)-aminopropyl methyl dimethoxysilane), NH
2(CH
2)
2nH (CH
2)
2nH (CH
2)
3siCH
3(OCH
3)
2(being called diethylenetriamine base propyl group methyl dimethoxysilane) and NH
2(CH
2)
2nH (CH
2)
2nH (CH
2)
3si (OCH
3)
3(being called diethylenetriamine base propyl trimethoxy silicane) can be used as the first silane coupling agent, commodity shown in the commercially available various above-mentioned chemical formula that can be used as silane coupling agent may be used to the present invention, and for example the trade mark purchased from Debang Chemical New Material Co., Ltd. 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 coupling agent is NH
2(CH
2)
2nH (CH
2)
3si (OCH
3)
3, NH
2(CH
2)
2nH (CH
2)
3si (OC
2h
5)
3and NH
2(CH
2)
2nH (CH
2)
3siCH
3(OCH
3)
2in at least one.
According to the preparation method of metallic surface provided by the invention chemical pretreatment solution, wherein, Cl (CH
2)
3si (OCH
3)
3(being called γ-r-chloropropyl trimethoxyl silane), Cl (CH
2)
3si (OC
2h
5)
3(being called γ-chloropropyl triethoxysilane), Cl (CH
2)
3siCH
3(OCH
3)
2(being called gamma-chloropropylmethyldimethoxysilane) and Cl (CH
2)
3siCH
3(OC
2h
5)
2(being called γ-chloropropyl methyldiethoxysilane) can be used as the second silane coupling agent, commodity shown in the commercially available various above-mentioned chemical formula that can be used as silane coupling agent may be used to the present invention, and for example the trade mark purchased from Debang Chemical New Material Co., Ltd. is the commercially available product of DB-231, DB-230, DB-221 and DB-220.Wherein, more preferably described the second silane coupling agent is Cl (CH
2)
3si (OCH
3)
3(being called γ-r-chloropropyl trimethoxyl silane).
According to the preparation method of metallic surface provided by the invention chemical pretreatment solution, wherein, described water-soluble silicate can be water glass and/or potassium silicate.Described water glass can be at least one in anhydrous sodium metasilicate, SODIUM METASILICATE PENTAHYDRATE and nine water water glass.And the consumption of described water-soluble silicate is to calculate with the amount of anhydrous silicate.
According to the preparation method of metallic surface provided by the invention chemical pretreatment solution, wherein, described cilicon oxide filler does not have special requirement, can be for take the various fillers that silicon oxide is main body, for example, described cilicon oxide filler can be nano-silica powder and/or nano silicon dioxide sol; Under preferable case, the particle diameter of the silicon oxide in described cilicon oxide filler can be 5-90nm, 5-30nm more preferably, for example, can use the commercially available product that the trade mark purchased from Asahi Denka Co., Ltd. is AT-30, AT-30S, AT-40, AT-30A and AT-20, or be the commercially available product of SS-25 and SS-30 purchased from the trade mark of Shandong Bai Te novel material company limited.And, the consumption of cilicon oxide filler is to calculate with the weight of silicon oxide itself, for example the consumption of nano silicon dioxide sol is to calculate with the amount of the silicon-dioxide in colloidal sol, and the weight with nano silicon dioxide sol is multiplied by the numerical evaluation obtaining after its dioxide-containing silica percentage ratio (weight).
According to the preparation method of metallic surface provided by the invention chemical pretreatment solution, wherein, described water-soluble film-forming resin can be for various water miscible and can be used in modification or the unmodified resin of film forming, described resin can be used with suitable goods form, water-soluble emulsion for example, at least one in water-soluble solution and water-soluble solid, the present invention does not have special requirement, as long as the film forming of can be used in, for example, described water-soluble film-forming resin can be the water-soluble polyester film-forming resin (water-soluble film-forming resin being obtained by polyalcohols monomer and polynary acids monomer polymerization, for example, purchased from Guangzhou Lapo Fine Chemicals Co., Ltd., the vibrin of trade mark CB2200), water-soluble phenylpropyl alcohol film-forming resin (by styrene monomer and vinylformic 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 is the benzene emulsion of xy-108b), soluble epoxide film-forming resin (the water-soluble film-forming resin being obtained by the monomer polymerization that contains epoxy group(ing), for example, purchased from Dongguan City Heima Chemical Co., Ltd., the trade mark is the epoxy resin of BH620), aqurous ployurethane film-forming resin (by multicomponent isocyanate class monomer and multi-hydroxy compounds monomer polymerization and water-soluble film-forming resin, for example, purchased from Jinjiang, Fujian Province Jian Hua company, the urethane resin of the trade mark 812), water-soluble silicon the third film-forming resin (by silicone based monomer and vinylformic acid (ester) class monomer polymerization and water-soluble film-forming resin, the Qingdao paint company TC-05 type organosilicon crylic acid latex of making the country prosperous for example, solid content is 48 % by weight), water-soluble acrylic film-forming resin (the water-soluble film-forming resin being obtained by vinylformic acid (ester) class monomer polymerization, the acrylic resin that is for example A-3418 purchased from the trade mark of Guangzhou Ou Peng chemical industry) and the water-soluble fluorine carbon film-forming resin (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 at least one in water-soluble phenylpropyl alcohol film-forming resin, soluble epoxide film-forming resin, water-soluble silicon the third film-forming resin, water-soluble acrylic film-forming resin, aqurous ployurethane film-forming resin and water-soluble polyester film-forming resin.More preferably, wherein, described water-soluble silicon the third film-forming resin is Silomer8861 emulsion (purchased from Richdale Special Chemicals Inc., Rui De special chemical company).
According to the preparation method of metallic surface provided by the invention chemical pretreatment solution, wherein, in order further to improve the lubricity of the protective film forming, under preferable case, this preparation method also comprises: the material after water and silane coupling agent are mixed mixes with lubricating auxiliary agent, one or more in the water-based emulsion that described lubricating auxiliary agent is dimethyl silicone oil, polyether-modified polysiloxane, the water-based emulsion of polyethylene wax and the water-based emulsion of oxidized polyethlene wax.
More preferably, with respect to the described water-soluble silicate of 1 weight part, the content of described lubricating auxiliary agent is 0.2-1.8 weight part, more preferably 0.5-0.7 weight part.
Wherein, the solid content of the water-based emulsion of described dimethyl silicone oil can be 10-90 % by weight, is preferably 30-80 % by weight.It should be noted that, the water-based emulsion of dimethyl silicone oil is when preparing metallic surface provided by the invention chemical pretreatment solution, and 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, the solid content of the water-based emulsion of described dimethyl silicone oil refers to the content of the dimethyl silicone oil that the water-based emulsion of the described dimethyl silicone oil of preparation is used.Described dimethyl silicone oil refers to water-insoluble unmodified dimethyl silicone oil.
Wherein, the dimethyl-silicon oil viscosity in the water-based emulsion of described dimethyl silicone oil can be 500-50000mPaS, is preferably 1000-40000mPaS, more preferably 1500-30000mPaS.
Wherein, described polyether-modified polysiloxane is commonly called as water-soluble dimethyl silicone oil, and existing various water-soluble dimethyl 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-modified polysiloxane is that viscosity is 100-10000mPaS, is preferably 500-8000mPaS, and 1000-6000mPaS more preferably is further preferably the water-soluble dimethyl silicone oil of 2000-5000mPaS.
It should be noted that, in the present invention, do not do in the situation of contrary explanation, described viscosity refers to the apparent viscosity numerical value recording at 25 ℃.
Wherein, the water-based emulsion of described polyethylene wax can be according to ordinary method by the water-based emulsion obtaining after polyethylene wax emulsification, the solid content of the water-based emulsion of described polyethylene wax can be 30-60 % by weight, is preferably 40-50 % by weight.It should be noted that, the water-based emulsion of polyethylene wax is when preparing metallic surface provided by the invention chemical pretreatment solution, and 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 polyethylene wax in the water-based emulsion of described polyethylene wax can be 90-130 ℃, is preferably 100-120 ℃, more preferably 105-115 ℃.
Wherein, the water-based emulsion of described oxidized polyethlene wax can be according to ordinary method by the water-based emulsion obtaining after oxidized polyethlene wax emulsification, the solid content of the water-based emulsion of described oxidized polyethlene wax can be 30-60 % by weight, is preferably 40-50 % by weight.It should be noted that, the water-based emulsion of oxidized polyethlene wax is when preparing metallic surface provided by the invention chemical pretreatment solution, and 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 oxidized polyethlene wax in the water-based emulsion of described oxidized polyethlene wax can be 80-120 ℃, is preferably 90-115 ℃, more preferably 100-110 ℃.
It should be noted that, in the present invention, do not do in the situation of contrary explanation, the fusing point of polyethylene wax and oxidized polyethlene wax refers to the numerical value of measuring according to mensuration-cooling curve method of GB/T2539-2008 petroleum wax fusing point.
Wherein, the acid number of the oxidized polyethlene wax in the water-based emulsion of described oxidized polyethlene wax can be 5-60mgKOH/g, is preferably 10-50mgKOH/g.Wherein, described acid number is the numerical value of measuring according to GB/T264-83 petroleum product acid value measuring method.
The present invention also provides the metallic surface preparing according to preparation method as above chemical pretreatment solution.Wherein, in preparation method as above, obtain added water-soluble film-forming resin and mix after material (that is the uniform liquid E, obtaining) can be used as metallic surface of the present invention chemical pretreatment solution and use.
In addition, metallic surface of the present invention chemical pretreatment solution can also contain other various components that do not affect metallic surface chemical pretreatment solution character, as one or more in dyestuff, pigment, dispersion agent and defoamer.The gross weight of this metallic surface chemical pretreatment solution of take 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 can be various defoamer well known in the art, such as one or more in polyethers defoamer, higher alcohols defoamer and silicon defoamer etc.More particularly, described defoamer can be for being purchased one or more in the SD-401 of limited liability company of the large Creative Science and Technology Co. Ltd of Dongying dan for example series defoamer.Under preferable case, the total amount of described metallic surface chemical pretreatment solution of take is benchmark, and the content of described defoamer is 0.01-0.05 % by weight.
Correspondingly, the preparation method of metallic surface provided by the invention chemical pretreatment solution can also comprise and adds other the various component of metallic surface chemical pretreatment solution character steps that mix of not affecting.These other various components that do not affect metallic surface chemical pretreatment solution character can add after adding water-soluble film-forming resin again.
Metallic surface of the present invention chemical pretreatment solution can directly be used without dilution.
The present invention also provides the purposes of above-mentioned metallic surface chemical pretreatment solution in preparing metallic substance.Above-mentioned metallic surface chemical pretreatment solution can be in the mode of this area routine for the preparation of various metallic substance.
According to hot-dip metal plated material provided by the invention, this hot-dip metal plated material comprises pot galvanize metal base and is attached to the coating on this hot-dip metal plated base material, described hot-dip metal plated base material is at least one in pot galvanize metal base, hot-dip aluminizing zinc metal base and hot-dip aluminizing zinc magnesium metal base material, and described coating is the cured product of metallic surface as above chemical pretreatment solution.
Wherein, described pot galvanize metal base can be for containing the metal base of zinc coating, and in described zinc coating, the content of zinc 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 for containing the metal base of zinc-aluminium coating, and 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 contain other conventional ingredient, as silicon.
Wherein, hot-dip aluminizing zinc magnesium metal base material can be for containing the metal base of aluminium zinc-magnesium coating, and in described aluminium zinc-magnesium coating, 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 the conventional thickness of the erosion shield on hot-dip metal plated base material, in order to improve the performance of described coating, under preferable case, the thickness of described coating is 0.05-2 micron, can be preferably 0.1-1 micron.Wherein, the thickness of coating is to use XRF(fluorescence spectrophotometer) numerical value measured of survey meter.
According to hot-dip metal plated material provided by the invention, wherein, the method of adhering to described coating on hot-dip metal plated base material can comprise described metallic surface chemical pretreatment solution is attached on the surface of hot-dip metal plated base material, then dry, dry temperature can be 60-120 ℃, be preferably 90-110 ℃, the time can be 0.5-3 second.The consumption of described metallic surface chemical pretreatment solution can be determined according to the thickness of coating.
Wherein, described dry method, can be one or more in warm air drying, induction heating and infrared radiation heating.
In the present invention, do not do in the situation of contrary explanation, the volume of all liquid and solid all refers to 20 ℃, the volume that 1 standard atmosphere is depressed.
Below will to the present invention, be explained in further detail by embodiment.
Embodiment 1
The silane coupling agent of the water of 28 weight parts and 1.6 weight parts (being comprised of the first silane coupling agent and the second silane coupling agent) is mixed to evenly under the stirring velocity of 1500 revs/min, obtains uniform liquid A, wherein, the first silane coupling agent is NH
2(CH
2)
2nH (CH
2)
3si (OCH
3)
3, purchased from Debang Chemical New Material Co., Ltd., trade mark DB-792, the second silane coupling agent is Cl (CH
2)
3si (OCH
3)
3, purchased from Debang Chemical New Material Co., Ltd., trade mark DB-231, the weight ratio of the first silane coupling agent and the second silane coupling agent is 1:0.5.
The water-soluble silicate of whole uniform liquid A and 1 weight part (metasilicate pentahydrate sodium, purchased from Qingdao great Run Chemical Co., Ltd.) is mixed to evenly under the stirring velocity of 1500 revs/min, obtains uniform liquid B.
The promotor (thiocarbamide) of whole uniform liquid B and 0.6 weight part is mixed to evenly under the stirring velocity of 1500 revs/min, obtains uniform liquid C.
By the cilicon oxide filler (nano silicon dioxide sol of whole uniform liquid C and 0.72 weight part, purchased from Shandong Bai Te novel material company limited, the trade mark is SS-30, and weight is in silicon-dioxide) under the stirring velocity of 1500 revs/min, be mixed to evenly, obtain uniform liquid D.
By the water-soluble film-forming resin of whole uniform liquid D and 2.4 weight parts (in solid), ((Silomer8861 emulsion is (purchased from Richdale Special Chemicals Inc. for water-soluble silicon the third film-forming resin, Rui De special chemical company, solid content is 43 % by weight))) under the stirring velocity of 1500 revs/min, be mixed to evenly, obtain uniform liquid E.Uniform liquid E is the metallic surface chemical pretreatment solution of the present embodiment.
Comparative example 1
According to the method for embodiment 1, prepare metallic surface chemical pretreatment solution, different is, in mixing container used, first add water, silane coupling agent, water-soluble silicate, promotor, cilicon oxide filler and water-soluble film-forming resin simultaneously, under the stirring velocity of 1500 revs/min, be mixed to again evenly, obtain the metallic surface chemical pretreatment solution of this comparative example.
Comparative example 2
According to the method for embodiment 1, prepare metallic surface chemical pretreatment solution, different is, water, water-soluble film-forming resin, water-soluble silicate, promotor, cilicon oxide filler and silane coupling agent are mixed successively, obtain the metallic surface chemical pretreatment solution of this comparative example.That is, the application of sample order of silane coupling agent and water-soluble film-forming resin is exchanged.
Comparative example 3
According to the method for embodiment 1, prepare metallic surface chemical pretreatment solution, different is, water, silane coupling agent, cilicon oxide filler, promotor, water-soluble silicate and water-soluble film-forming resin are mixed successively, obtain the metallic surface chemical pretreatment solution of this comparative example.That is, the application of sample order of water-soluble silicate and cilicon oxide filler is exchanged.
Comparative example 4
According to the method for embodiment 1, prepare metallic surface chemical pretreatment solution, different, the silane coupling agent of 1.6 weight parts is all the first silane coupling agent, does not contain the second silane coupling agent.
Comparative example 5
According to the method for embodiment 1, prepare metallic surface chemical pretreatment solution, different, the silane coupling agent of 1.6 weight parts is all the second silane coupling agent, does not contain the first silane coupling agent.
Embodiment 2
The silane coupling agent of the water of 25 weight parts and 1.4 weight parts (being comprised of the first silane coupling agent and the second silane coupling agent) is mixed to evenly under the stirring velocity of 1500 revs/min, obtains uniform liquid A, wherein, the first silane coupling agent is NH
2(CH
2)
2nH (CH
2)
3si (OC
2h
5)
3, purchased from Debang Chemical New Material Co., Ltd., trade mark DB-793, the second silane coupling agent is Cl (CH
2)
3si (OCH
3)
3, purchased from Debang Chemical New Material Co., Ltd., trade mark DB-231, the weight ratio of the first silane coupling agent and the second silane coupling agent is 1:0.4.
The water-soluble silicate of whole uniform liquid A and 1 weight part (potassium silicate, purchased from Baoding Run Feng Industrial Co., Ltd.) is mixed to evenly under the stirring velocity of 1500 revs/min, obtains uniform liquid B.
The promotor of whole uniform liquid B and 0.5 weight part (thiocarbamide and urea etc. weight mixture) is mixed to evenly under the stirring velocity of 1500 revs/min, obtains uniform liquid C.
The cilicon oxide filler of whole uniform liquid C and 0.6 weight part (nano silicon dioxide sol, purchased from Asahi Denka Co., Ltd., the trade mark is AT-30, weight is in silicon-dioxide) is mixed to evenly under the stirring velocity of 1500 revs/min, obtains uniform liquid D.
By the water-soluble film-forming resin of whole uniform liquid D and 2.1 weight parts (in solid), ((Silomer8861 emulsion is (purchased from Richdale Special Chemicals Inc. for water-soluble silicon the third film-forming resin, Rui De special chemical company, solid content is 43 % by weight))) under the stirring velocity of 1500 revs/min, be mixed to evenly, obtain uniform liquid E.Uniform liquid E is the metallic surface chemical pretreatment solution of the present embodiment.
Embodiment 3
The silane coupling agent of the water of 40 weight parts and 1.8 weight parts (being comprised of the first silane coupling agent and the second silane coupling agent) is mixed to evenly under the stirring velocity of 1500 revs/min, obtains uniform liquid A, wherein, the first silane coupling agent is NH
2(CH
2)
2nH (CH
2)
3siCH
3(OCH
3)
2, purchased from Debang Chemical New Material Co., Ltd., trade mark DB-602, the second silane coupling agent is Cl (CH
2)
3si (OCH
3)
3, purchased from Debang Chemical New Material Co., Ltd., trade mark DB-231, the weight ratio of the first silane coupling agent and the second silane coupling agent is 1:0.6.
The water-soluble silicate of whole uniform liquid A and 1 weight part (metasilicate pentahydrate sodium, purchased from Qingdao great Run Chemical Co., Ltd.) is mixed to evenly under the stirring velocity of 1500 revs/min, obtains uniform liquid B.
The promotor (urea) of whole uniform liquid B and 0.7 weight part is mixed to evenly under the stirring velocity of 1500 revs/min, obtains uniform liquid C.
The cilicon oxide filler of whole uniform liquid C and 0.85 weight part (nano silicon dioxide sol, purchased from Asahi Denka Co., Ltd., the trade mark is AT-30, weight is in silicon-dioxide) is mixed to evenly under the stirring velocity of 1500 revs/min, obtains uniform liquid D.
By the water-soluble film-forming resin of whole uniform liquid D and 2.7 weight parts (in solid), ((Silomer8861 emulsion is (purchased from Richdale Special Chemicals Inc. for water-soluble silicon the third film-forming resin, Rui De special chemical company, solid content is 43 % by weight))) under the stirring velocity of 1500 revs/min, be mixed to evenly, obtain uniform liquid E.Uniform liquid E is the metallic surface chemical pretreatment solution of the present embodiment.
Embodiment 4
The silane coupling agent of the water of 90 weight parts and 0.6 weight part (being comprised of the first silane coupling agent and the second silane coupling agent) is mixed to evenly under the stirring velocity of 1500 revs/min, obtains uniform liquid A, wherein, the first silane coupling agent is NH
2(CH
2)
2nH (CH
2)
3si (OCH
3)
3, purchased from Debang Chemical New Material Co., Ltd., trade mark DB-792, the second silane coupling agent is Cl (CH
2)
3si (OCH
3)
3, purchased from Debang Chemical New Material Co., Ltd., trade mark DB-231, the weight ratio of the first silane coupling agent and the second silane coupling agent is 1:0.4.
The water-soluble silicate of whole uniform liquid A and 1 weight part (metasilicate pentahydrate sodium, purchased from Qingdao great Run Chemical Co., Ltd.) is mixed to evenly under the stirring velocity of 1500 revs/min, obtains uniform liquid B.
The promotor (thiocarbamide) of whole uniform liquid B and 0.3 weight part is mixed to evenly under the stirring velocity of 1500 revs/min, obtains uniform liquid C.
By the cilicon oxide filler (nano silicon dioxide sol of whole uniform liquid C and 2.1 weight parts, purchased from Shandong Bai Te novel material company limited, the trade mark is SS-30, and weight is in silicon-dioxide) under the stirring velocity of 1500 revs/min, be mixed to evenly, obtain uniform liquid D.
By the water-soluble film-forming resin of whole uniform liquid D and 6.5 weight parts (in solid), ((Silomer8861 emulsion is (purchased from Richdale Special Chemicals Inc. for water-soluble silicon the third film-forming resin, Rui De special chemical company, solid content is 43 % by weight))) under the stirring velocity of 1500 revs/min, be mixed to evenly, obtain uniform liquid E.Uniform liquid E is the metallic surface chemical pretreatment solution of the present embodiment.
Embodiment 5
The silane coupling agent of the water of 15 weight parts and 4.5 weight parts (being comprised of the first silane coupling agent and the second silane coupling agent) is mixed to evenly under the stirring velocity of 1500 revs/min, obtains uniform liquid A, wherein, the first silane coupling agent is NH
2(CH
2)
2nH (CH
2)
3si (OCH
3)
3, purchased from Debang Chemical New Material Co., Ltd., trade mark DB-792, the second silane coupling agent is Cl (CH
2)
3si (OCH
3)
3, purchased from Debang Chemical New Material Co., Ltd., trade mark DB-231, the weight ratio of the first silane coupling agent and the second silane coupling agent is 1:0.6.
The water-soluble silicate of whole uniform liquid A and 1 weight part (metasilicate pentahydrate sodium, purchased from Qingdao great Run Chemical Co., Ltd.) is mixed to evenly under the stirring velocity of 1500 revs/min, obtains uniform liquid B.
The promotor (thiocarbamide) of whole uniform liquid B and 1.7 weight parts is mixed to evenly under the stirring velocity of 1500 revs/min, obtains uniform liquid C.
By the cilicon oxide filler (nano silicon dioxide sol of whole uniform liquid C and 0.3 weight part, purchased from Shandong Bai Te novel material company limited, the trade mark is SS-30, and weight is in silicon-dioxide) under the stirring velocity of 1500 revs/min, be mixed to evenly, obtain uniform liquid D.
By the water-soluble film-forming resin of whole uniform liquid D and 1.0 weight parts (in solid), ((Silomer8861 emulsion is (purchased from Richdale Special Chemicals Inc. for water-soluble silicon the third film-forming resin, Rui De special chemical company, solid content is 43 % by weight))) under the stirring velocity of 1500 revs/min, be mixed to evenly, obtain uniform liquid E.Uniform liquid E is the metallic surface chemical pretreatment solution of the present embodiment.
Embodiment 6
According to the method for embodiment 1, prepare metallic surface chemical pretreatment solution, different, the first silane coupling agent is NH
2(CH
2)
2nHCH
2cH (CH
3) CH
2cH
3(OCH
3)
2(purchased from Debang Chemical New Material Co., Ltd., trade mark DB-604).
Embodiment 7
According to the method for embodiment 1, prepare metallic surface chemical pretreatment solution, different, the first silane coupling agent is HO (CH
2)
2nH (CH
2)
2nH (CH
2)
3siCH
3(OCH
3)
2(purchased from Debang Chemical New Material Co., Ltd., trade mark DB-2602).
Embodiment 8
According to the method for embodiment 1, prepare metallic surface chemical pretreatment solution, different, the first silane coupling agent is NH
2(CH
2)
2nH (CH
2)
2nH (CH
2)
3siCH
3(OCH
3)
2(purchased from Debang Chemical New Material Co., Ltd., trade mark DB-5551).
Embodiment 9
According to the method for embodiment 1, prepare metallic surface chemical pretreatment solution, different, the second silane coupling agent is Cl (CH
2)
3si (OC
2h
5)
3(purchased from Debang Chemical New Material Co., Ltd., trade mark DB-230).
Embodiment 10
According to the method for embodiment 1, prepare metallic surface chemical pretreatment solution, different, the second silane coupling agent is Cl (CH
2)
3siCH
3(OCH
3)
2(purchased from Debang Chemical New Material Co., Ltd., trade mark DB-221).
Embodiment 11
According to the method for embodiment 1, prepare metallic surface chemical pretreatment solution, different, the second silane coupling agent is Cl (CH
2)
3siCH
3(OC
2h
5)
2(purchased from Debang Chemical New Material Co., Ltd., trade mark DB-220).
Embodiment 12
According to the method for embodiment 1, prepare metallic surface chemical pretreatment solution, different, the weight ratio of the first silane coupling agent and the second silane coupling agent is 1:0.1.
Embodiment 13
According to the method for embodiment 1, prepare metallic surface chemical pretreatment solution, different, the weight ratio of the first silane coupling agent and the second silane coupling agent is 1:1.
Embodiment 14
According to the method for embodiment 1, prepare metallic surface chemical pretreatment solution; different is; use water-soluble silicon the third film-forming resin (Qingdao paint company TC-05 type organosilicon crylic acid latex of making the country prosperous; solid content is 48 % by weight) as water-soluble film-forming resin, and (water-based emulsion of dimethyl silicone oil and polyether-modified polysiloxane are by weight 1 in the material after water and silane coupling agent are mixed, to add lubricating auxiliary agent; 1 obtains after mixing, and the water-based emulsion of dimethyl silicone oil is purchased from Nanjing Hua Tuo Chemical Co., Ltd., and the trade mark is HTR-1, and solid content is 30 % by weight, is to obtain after the dimethyl silicone oil emulsification that is 25000mPaS by the apparent viscosity at 25 ℃; Polyether-modified polysiloxane is purchased from Dongguan Acer dyeing and finishing auxiliaries for textile Co., Ltd., Factory, and the apparent viscosity at 25 ℃ is 3000mPaS) and mix, wherein, with respect to the water-soluble silicate of 1 weight part, the consumption of lubricating auxiliary agent is 0.6 weight part.
Embodiment 15
According to the method for embodiment 14, prepare metallic surface chemical pretreatment solution, different, do not add lubricating auxiliary agent.
Embodiment 16
According to the method for embodiment 1, prepare metallic surface chemical pretreatment solution, different is, use water-soluble phenylpropyl alcohol film-forming resin (purchased from Guangzhou Chao Long Chemical Industry Science Co., Ltd, the trade mark is the benzene emulsion of xy-108b) as water-soluble film-forming resin, and (water-based emulsion of polyethylene wax and the water-based emulsion of oxidized polyethlene wax obtain after 1:1 mixes in the material after water and silane coupling agent are mixed, to add lubricating auxiliary agent, the water-based emulsion of polyethylene wax is purchased from Dongguan City Hong Guang plastic material business department, solid content is 48 % by weight, the fusing point of polyethylene wax is 110-115 ℃, the water-based emulsion of oxidized polyethlene wax is purchased from Beijing Zhong Guan special wax company limited, solid content is 48 % by weight, the fusing point of oxidized polyethlene wax is 105-110 ℃, acid number is 14-21mgKOH/g) and mix, wherein, with respect to the water-soluble silicate of 1 weight part, the consumption of lubricating auxiliary agent is 0.5 weight part.
Embodiment 17
According to the method for embodiment 1, prepare metallic surface chemical pretreatment solution, different is, use soluble epoxide film-forming resin (purchased from Dongguan City Heima Chemical Co., Ltd., the trade mark is the aqueous epoxy resin emulsion of BH620) as water-soluble film-forming resin, and add the lubricating auxiliary agent (water-based emulsion of dimethyl silicone oil in the material after water and silane coupling agent are mixed, purchased from Guangzhou Si Luoke Chemical Co., Ltd., solid content is 80 % by weight, to obtain after the dimethyl silicone oil emulsification that is 1500mPaS by the apparent viscosity at 25 ℃) and mix, wherein, water-soluble silicate with respect to 1 weight part, the consumption of lubricating auxiliary agent is 0.7 weight part.
Embodiment 18
According to the method for embodiment 1, prepare metallic surface chemical pretreatment solution, different is, use water-soluble polyester film-forming resin (purchased from Yancheng, Jiangsu Province Ju Ke Chemical Co., Ltd., the trade mark is the waterborne polyester of PE-10030-P) as water-soluble film-forming resin, and add the lubricating auxiliary agent (water-based emulsion of dimethyl silicone oil in the material after water and silane coupling agent are mixed, purchased from Guangzhou Si Luoke Chemical Co., Ltd., solid content is 80 % by weight, to obtain after the dimethyl silicone oil emulsification that is 1500mPaS by the apparent viscosity at 25 ℃) and mix, wherein, water-soluble silicate with respect to 1 weight part, the consumption of lubricating auxiliary agent is 0.7 weight part.
Preparation Example 1
Get the metallic surface chemical pretreatment solution that embodiment 1-18 and comparative example 1-5 obtain and be coated on respectively steel plate galvanized (purchased from Pangang Group Panzhihua Steel Vanadium Co., Ltd., model DX54D, in zinc coating containing zinc 95 % by weight) surface, at 90-110 ℃, warm air drying is 2 seconds, the steel plate galvanized after being processed respectively.Wherein, coating amount makes the thickness of the coating on the steel plate galvanized after processing be 0.8 micron.The thickness of coating is to use XRF(fluorescence spectrophotometer) numerical value measured of survey meter.Wherein, the metallic surface chemical pretreatment solution using in this Preparation Example is all to have stored the metallic surface chemical pretreatment solution of 1 day after having prepared (obtaining uniform liquid E).
Preparation Example 2-4
Steel plate galvanized after processing according to the method preparation of Preparation Example 1, different, the metallic surface chemical pretreatment solution of use is all to have stored the metallic surface chemical pretreatment solution of 60,120 and 180 days after having prepared (obtaining uniform liquid E).
Test implementation example 1
By the requirement of stipulating in GB/T101251997, carry out neutral salt spray test, measure respectively the corrosion resisting property of the steel plate galvanized after the processing of Preparation Example 1-4.It is qualified by " salt-fog test 168h, corrosion area < 3% ", to be considered as.
On M-2000 ring block type friction and wear tester, the kinetic friction coefficient of the coating of the steel plate galvanized after the processing obtaining according to its specification sheets mensuration Preparation Example 1.
Test result as above is as shown in table 1.Number of days in bracket represents the storage time of metallic surface chemical pretreatment solution.
Visible according to the data of table 1, the solidity to corrosion of the protective film that metallic surface provided by the invention chemical pretreatment solution forms is very good, and the storage endurance of metallic surface provided by the invention chemical pretreatment solution is also very good.And, visible according to the data of table 1, at the preferred described water-soluble silicate with respect to 1 weight part, the content of described promotor is 0.5-0.7 weight part, the consumption of described silane coupling agent is 1.4-1.8 weight part, the weight ratio of the first silane coupling agent and described the second silane coupling agent is 1:0.4-6, the consumption of described cilicon oxide filler is 0.6-0.85 weight part, in solid, the consumption of described water-soluble film-forming resin is 2.1-2.7 weight part, the consumption of water is in the situation of 25-40 weight part, can further improve the solidity to corrosion of the protective film of described metallic surface chemical pretreatment solution formation.And, visible according to the data of table 1, in the situation that preferred described water-soluble silicon the third film-forming resin is Silomer8861 emulsion, or preferred described raw mixture also contains in the situation of lubricating auxiliary agent, can further improve the oilness of the protective film that described metallic surface chemical pretreatment solution forms.In addition according to the data of table 1, at preferred described the first silane coupling agent, be NH,
2(CH
2)
2nH (CH
2)
3si (OCH
3)
3, NH
2(CH
2)
2nH (CH
2)
3si (OC
2h
5)
3and NH
2(CH
2)
2nH (CH
2)
3siCH
3(OCH
3)
2in at least one, preferably described the second silane coupling agent is Cl (CH
2)
3si (OCH
3)
3situation under, can further improve the solidity to corrosion of the protective film that described metallic surface chemical pretreatment solution forms.
Table 1
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characterictic described in above-mentioned embodiment, in reconcilable situation, can combine by any suitable mode, for fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible array modes.
In addition, between various embodiment of the present invention, also can carry out arbitrary combination, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. a preparation method for metallic surface chemical pretreatment solution, the method comprises water, silane coupling agent, water-soluble silicate, promotor, cilicon oxide filler and water-soluble film-forming resin is mixed successively; Described silane coupling agent comprises the first silane coupling agent and the second silane coupling agent, and described the first silane coupling agent is R-Si (OCH
3)
3, R-Si (OC
2h
5)
3, R-SiCH
3(OCH
3)
2and R-SiCH
3(OC
2h
5)
2in at least one, and R is selected from NH independently of one another
2(CH
2)
2nH (CH
2)
3-, NH
2(CH
2)
2nHCH
2cH (CH
3) CH
2-, HO (CH
2)
2nH (CH
2)
2nH (CH
2)
3-or NH
2(CH
2)
2nH (CH
2)
2nH (CH
2)
3-; Described the second silane coupling agent is Cl (CH
2)
3si (OCH
3)
3, Cl (CH
2)
3si (OC
2h
5)
3, Cl (CH
2)
3siCH
3(OCH
3)
2and Cl (CH
2)
3siCH
3(OC
2h
5)
2in at least one; Described promotor is thiocarbamide and/or urea.
2. preparation method according to claim 1, wherein, described water-soluble silicate with respect to 1 weight part, the consumption of described promotor is 0.2-1.8 weight part, the consumption of described silane coupling agent is 0.5-4.5 weight part, the weight ratio of described the first silane coupling agent and described the second silane coupling agent is 1:0.1-1, the consumption of described cilicon oxide filler is 0.25-2.2 weight part, in solid, the consumption of described water-soluble film-forming resin is 0.8-6.8 weight part, the consumption of water is 10-100 weight part, preferably, described water-soluble silicate with respect to 1 weight part, the consumption of described promotor is 0.5-0.7 weight part, the consumption of described silane coupling agent is 1.4-1.8 weight part, the weight ratio of described the first silane coupling agent and described the second silane coupling agent is 1:0.4-0.6, the consumption of described cilicon oxide filler is 0.6-0.85 weight part, in solid, the consumption of described water-soluble film-forming resin is 2.1-2.7 weight part, the consumption of water is 25-40 weight part.
3. preparation method according to claim 1 and 2, wherein, described the first silane coupling agent is NH
2(CH
2)
2nH (CH
2)
3si (OCH
3)
3, NH
2(CH
2)
2nH (CH
2)
3si (OC
2h
5)
3, NH
2(CH
2)
2nH (CH
2)
3siCH
3(OCH
3)
2, NH
2(CH
2)
2nHCH
2cH (CH
3) CH
2cH
3(OCH
3)
2, HO (CH
2)
2nH (CH
2)
2nH (CH
2)
3siCH
3(OCH
3)
2, NH
2(CH
2)
2nH (CH
2)
2nH (CH
2)
3siCH
3(OCH
3)
2and NH
2(CH
2)
2nH (CH
2)
2nH (CH
2)
3si (OCH
3)
3in at least one.
4. preparation method according to claim 1 and 2, wherein, described the second silane coupling agent is Cl (CH
2)
3si (OCH
3)
3.
5. preparation method according to claim 1 and 2, wherein, described water-soluble film-forming resin is at least one in water-soluble polyester film-forming resin, water-soluble phenylpropyl alcohol film-forming resin, soluble epoxide film-forming resin, aqurous ployurethane film-forming resin, water-soluble silicon the third film-forming resin, water-soluble acrylic film-forming resin and water-soluble fluorine carbon film-forming resin, wherein, described water-soluble silicon the third film-forming resin is preferably Silomer8861 emulsion.
6. preparation method according to claim 1 and 2, wherein, this preparation method also comprises: the material after water and silane coupling agent are mixed mixes with lubricating auxiliary agent, described lubricating auxiliary agent is the water-based emulsion of dimethyl silicone oil, one or more in polyether-modified polysiloxane, the water-based emulsion of polyethylene wax and the water-based emulsion of oxidized polyethlene wax, with respect to the described water-soluble silicate of 1 weight part, the consumption of described lubricating auxiliary agent is 0.2-1.8 weight part.
7. the metallic surface chemical pretreatment solution that in claim 1-6, the preparation method described in any one prepares.
8. the purposes of metallic surface claimed in claim 7 chemical pretreatment solution in preparing metallic substance.
9. a hot-dip metal plated material, this hot-dip metal plated material comprises hot-dip metal plated base material and is attached to the coating on this hot-dip metal plated base material, described hot-dip metal plated base material is at least one in pot galvanize metal base, hot-dip aluminizing zinc metal base and hot-dip aluminizing zinc magnesium metal base material, it is characterized in that, described coating is the cured product of metallic surface claimed in claim 7 chemical pretreatment solution.
10. hot-dip metal plated material according to claim 9, wherein, the thickness of described coating is 0.1-1 micron.
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| CN108914105A (en) * | 2018-07-19 | 2018-11-30 | 苏州瑞沁精密机械有限公司 | A kind of die surface treatment fluid |
| CN117779030A (en) * | 2024-01-10 | 2024-03-29 | 开平和盟环保科技有限公司 | Silicon crystal tank liquid and environment-friendly metal surface treatment process |
| CN117779030B (en) * | 2024-01-10 | 2024-05-17 | 开平和盟环保科技有限公司 | Silicon crystal tank liquid and environment-friendly metal surface treatment process |
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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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| 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 |
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| CN108914105A (en) * | 2018-07-19 | 2018-11-30 | 苏州瑞沁精密机械有限公司 | A kind of die surface treatment fluid |
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| CN117779030B (en) * | 2024-01-10 | 2024-05-17 | 开平和盟环保科技有限公司 | Silicon crystal tank liquid and environment-friendly metal surface treatment process |
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