CN103509441A - Metal protective paint and application thereof, and hot-dip metal material - Google Patents
Metal protective paint and application thereof, and hot-dip metal material Download PDFInfo
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- CN103509441A CN103509441A CN201210220576.XA CN201210220576A CN103509441A CN 103509441 A CN103509441 A CN 103509441A CN 201210220576 A CN201210220576 A CN 201210220576A CN 103509441 A CN103509441 A CN 103509441A
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Abstract
The invention provides a metal protective paint which is prepared by uniformly mixing a raw material mixture, wherein the raw material mixture contains water-soluble silicate, silicon oxide filler, accelerator, water-soluble film-forming resin, N-beta-aminoethyl-gamma-aminopropyl silane coupling agent and water. The invention also provides application of the metal protective paint in preparation of metal materials. The invention also provides a hot-dip metal material which comprises a hot-dip metal substrate and a coating attached to the hot-dip metal substrate, wherein the coating is the cured product of the metal protective paint. The protective film formed by the metal protective paint provided by the invention has very excellent corrosion resistance, water resistance, heat resistance and fingerprint resistance.
Description
Technical field
The present invention relates to metal protection field, particularly, relate to a kind of metal protection coating, the purposes of this metal protection coating and a kind of hot-dip metal plated material.
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 protective coating to form protective film.Thereby the performance of metal protection coating is very important for the rust protection of hot-dip metal plated material.
For example, CN101608306A discloses a kind of passivating solution, also belongs to a kind of metal protection coating, 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, and wherein, described water soluble organic substance is the mixture of alcohol and organic carboxyl acid.
But the solidity to corrosion, water tolerance, thermotolerance and the anti-finger printing that experiment showed, the protective film that this metal protection coating forms are still poor.
Summary of the invention
The poor defect of solidity to corrosion, water tolerance, thermotolerance and anti-finger printing that the object of the invention is to overcome the protective film that existing metal protection coating forms, provides a kind of metal protection coating that can form solidity to corrosion, water tolerance, thermotolerance and the good protective film of anti-finger printing.
To achieve these goals, the invention provides a kind of metal protection coating, this metal protection coating obtains after being mixed by a kind of raw mixture, and described raw mixture contains water-soluble silicate, cilicon oxide filler, promotor, water-soluble film-forming resin, N-β-aminoethyl-γ-γ-aminopropylsilane coupling agent and water; Described promotor is contained the first promotor and/or the second promotor, and described the first promotor is at least one in pyrrolidone, N-Methyl pyrrolidone and N-ethyl pyrrolidone, and described the second promotor is thiocarbamide and/or urea; Described N-β-aminoethyl-γ-γ-aminopropylsilane coupling agent is NH
2(CH
2)
2nH (CH
2)
3si (OCH
2cH
3)
3, NH
2(CH
2)
2nH (CH
2)
3si (OCH
3)
3and NH
2(CH
2)
2nH (CH
2)
3siCH
3(OCH
3)
2in at least one.
The present invention also provides the purposes of above-mentioned metal protection coating 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 metal protection coating as above.
By technique scheme, solidity to corrosion, water tolerance, thermotolerance and the anti-finger printing of the protective film that metal protection coating provided by the invention forms are all very good.
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.
According to metal protection coating provided by the invention, wherein, this metal protection coating obtains after being mixed by a kind of raw mixture, and described raw mixture contains water-soluble silicate, cilicon oxide filler, promotor, water-soluble film-forming resin, N-β-aminoethyl-γ-γ-aminopropylsilane coupling agent and water; Described promotor is contained the first promotor and/or the second promotor, and described the first promotor is at least one in pyrrolidone, N-Methyl pyrrolidone and N-ethyl pyrrolidone, and described the second promotor is thiocarbamide and/or urea; Described N-β-aminoethyl-γ-γ-aminopropylsilane coupling agent is NH
2(CH
2)
2nH (CH
2)
3si (OCH
2cH
3)
3, NH
2(CH
2)
2nH (CH
2)
3si (OCH
3)
3and NH
2(CH
2)
2nH (CH
2)
3siCH
3(OCH
3)
2in at least one.
Wherein, NH
2(CH
2)
2nH (CH
2)
3si (OCH
2cH
3)
3(being called N-β-aminoethyl-γ-aminopropyl triethoxysilane), NH
2(CH
2)
2nH (CH
2)
3si (OCH
3)
3(being called N-β-aminoethyl-γ-aminopropyltrimethoxysilane) and NH
2(CH
2)
2nH (CH
2)
3siCH
3(OCH
3)
2(being called N-β-aminoethyl-γ-aminopropyl methyl dimethoxysilane), can be used as silane coupling agent, the 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.
Wherein, this metal protection coating is to obtain after described raw mixture mixes, and is the liquid of comparatively stable and homogeneous.Under preferable case, each component in described raw mixture mixes before use at this metal protection coating for 1-180 days.Wherein, the order by merging of each composition is not had to special requirement, can directly each component in described raw mixture be carried out simultaneously, mix in batches or step by step, as long as can obtain uniform stable phase, preferably by stirring, make to mix more even.
According to metal protection coating provided by the invention, wherein, with respect to the described water-soluble silicate of 1 weight part, the consumption of described N-β-aminoethyl-γ-γ-aminopropylsilane coupling agent can be 0.5-4.5 weight part, is preferably 1.4-1.8 weight part.
Wherein, with respect to the described water-soluble silicate of 1 weight part, the content of described promotor can be 0.2-1.8 weight part, is preferably 0.5-0.7 weight part.
Wherein, the weight ratio between described the first promotor and the second promotor does not have special requirement, and for example the weight ratio between described the first promotor and the second promotor can be 1:(0.5-2).
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 metal protection coating provided by the invention, wherein, in order further to improve the performance of described metal protection coating, under preferable case, described N-β-aminoethyl-γ-γ-aminopropylsilane coupling agent is NH
2(CH
2)
2nH (CH
2)
3si (OCH
2cH
3)
3, NH
2(CH
2)
2nH (CH
2)
3si (OCH
3)
3and NH
2(CH
2)
2nH (CH
2)
3siCH
3(OCH
3)
2by 1:(0.5-2): the mixture that weight ratio (0.5-2) is mixed to get.
According to metal protection coating provided by the invention, wherein, described water-soluble silicate can be water glass and/or potassium silicate.
According to metal protection coating provided by the invention, wherein, described cilicon oxide filler does not have special requirement, can be for take the various fillers that silicon oxide is main body, and for example, described cilicon oxide filler can be nano-silica powder and/or silicon sol; Under preferable case, described cilicon oxide filler is nano-silica powder, and the particle diameter of described nano-silica powder can be 10-90nm.
According to metal protection coating provided by the invention, 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 Silomer 8861 emulsions (purchased from Richdale Special Chemicals Inc. ，Rui De special chemical companies).
According to metal protection coating provided by the invention, wherein, in order further to improve the lubricity of the protective film forming, under preferable case, metal protection coating of the present invention also contains 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 metal protection coating provided by the invention, 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 metal protection coating provided by the invention, 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 metal protection coating provided by the invention, 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/T 2539-2008 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/T 264-83 petroleum product acid value measuring method.
Except containing mentioned component, metal protection coating of the present invention can also contain other various components that do not affect metal protection coating property, as one or more in dyestuff, pigment, dispersion agent and defoamer.The gross weight of this metal protection coating 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 metal protection coating of take is benchmark, and the content of described defoamer is 0.01-0.05 % by weight.
Metal protection coating of the present invention can directly be used without dilution.
The present invention also provides the purposes of above-mentioned metal protection coating in preparing metallic substance.Above-mentioned metal protection coating 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, it is characterized in that, described coating is the cured product of metal protection coating as above.
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 metallic substance 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.
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 metal protection coating 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 metal protection coating 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.In following examples and comparative example, each raw material of metal protection coating is substantially to add in container simultaneously.
Embodiment 1
By N-β-aminoethyl-γ-γ-aminopropylsilane coupling agent (NH of the promotor of the water-soluble silicate of 1 weight part (water glass, purchased from Baoding Run Feng Industrial Co., Ltd.), 0.6 weight part (pyrrolidone and the thiocarbamide mixture that 1:1 obtains after mixing by weight), 1.6 weight parts
2(CH
2)
2nH (CH
2)
3si (OCH
2cH
3)
3(purchased from Debang Chemical New Material Co., Ltd., trade mark DB-793, NH
2(CH
2)
2nH (CH
2)
3si (OCH
3)
3(purchased from Debang Chemical New Material Co., Ltd., trade mark DB-792) and NH
2(CH
2)
2nH (CH
2)
3siCH
3(OCH
3)
2(purchased from Debang Chemical New Material Co., Ltd., trade mark DB-602) etc. the mixture that weight is mixed to get), cilicon oxide filler (the nano-silica powder of 0.72 weight part, purchased from U.S. GE company, RNS-E, mean particle size 20nm), ((Silomer 8861 emulsions are (purchased from Richdale Special Chemicals Inc. for water-soluble silicon the third film-forming resin for the water-soluble film-forming resin of 2.4 weight parts (in solid), Rui De special chemical company, solid content is 43 % by weight))) and the water of 28 weight parts, under the stirring velocity of 1500 revs/min, be mixed to evenly, obtain the metal protection coating of the present embodiment.
Comparative example 1
According to the method for embodiment 1, prepare metal protection coating, different, with aminopropyl triethoxysilane (purchased from Hubei Li Meida fluosilicic Science and Technology Ltd., trade mark LMD-1100), replace N-β-aminoethyl-γ-γ-aminopropylsilane coupling agent.
Comparative example 2
According to the method for embodiment 1, prepare metal protection coating, different, do not add promotor.
Comparative example 3
According to the method for embodiment 1, prepare metal protection coating, different, do not add water-soluble silicate.
Comparative example 4
According to the method for embodiment 1, prepare metal protection coating, different, do not add cilicon oxide filler.
Embodiment 2
By the water-soluble silicate of 1 weight part (potassium silicate, purchased from Baoding Run Feng Industrial Co., Ltd.), the promotor (pyrrolidone) of 0.5 weight part, N-β-aminoethyl-γ-γ-aminopropylsilane coupling agent (NH of 1.4 weight parts
2(CH
2)
2nH (CH
2)
3si (OCH
2cH
3)
3(purchased from Debang Chemical New Material Co., Ltd., trade mark DB-793, NH
2(CH
2)
2nH (CH
2)
3si (OCH
3)
3(purchased from Debang Chemical New Material Co., Ltd., trade mark DB-792) and NH
2(CH
2)
2nH (CH
2)
3siCH
3(OCH
3)
2(purchased from Debang Chemical New Material Co., Ltd., trade mark DB-602) mixture being mixed to get according to the weight ratio of 1:0.5:2), cilicon oxide filler (the nano silicon of 0.6 weight part, purchased from U.S. GE company, RNS-E, mean particle size 20nm), ((Silomer 8861 emulsions are (purchased from Richdale Special Chemicals Inc. for water-soluble silicon the third film-forming resin for the water-soluble film-forming resin of 2.1 weight parts (in solid), Rui De special chemical company, solid content is 43 % by weight))) and the water of 25 weight parts, under the stirring velocity of 1500 revs/min, be mixed to evenly, obtain the metal protection coating of the present embodiment.
Embodiment 3
By the water-soluble silicate of 1 weight part (water glass, purchased from Baoding Run Feng Industrial Co., Ltd.), the promotor (thiocarbamide) of 0.7 weight part, N-β-aminoethyl-γ-γ-aminopropylsilane coupling agent (NH of 1.8 weight parts
2(CH
2)
2nH (CH
2)
3si (OCH
2cH
3)
3(purchased from Debang Chemical New Material Co., Ltd., trade mark DB-793, NH
2(CH
2)
2nH (CH
2)
3si (OCH
3)
3(purchased from Debang Chemical New Material Co., Ltd., trade mark DB-792) and NH
2(CH
2)
2nH (CH
2)
3siCH
3(OCH
3)
2(purchased from Debang Chemical New Material Co., Ltd., trade mark DB-602) mixture being mixed to get according to the weight ratio of 1:2:0.5), the cilicon oxide filler of the 0.85 weight part (silicon sol of 30 % by weight, usage quantity is in solid), ((Silomer 8861 emulsions are (purchased from Richdale Special Chemicals Inc. for water-soluble silicon the third film-forming resin for the water-soluble film-forming resin of 2.7 weight parts (in solid), Rui De special chemical company, solid content is 43 % by weight))) and the water of 40 weight parts, under the stirring velocity of 1500 revs/min, be mixed to evenly, obtain the metal protection coating of the present embodiment.
Embodiment 4
By N-β-aminoethyl-γ-γ-aminopropylsilane coupling agent (NH of the promotor of the water-soluble silicate of 1 weight part (water glass, purchased from Baoding Run Feng Industrial Co., Ltd.), 0.3 weight part (pyrrolidone and the thiocarbamide mixture that 1:1 obtains after mixing by weight), 0.6 weight part
2(CH
2)
2nH (CH
2)
3si (OCH
2cH
3)
3(purchased from Debang Chemical New Material Co., Ltd., trade mark DB-793, NH
2(CH
2)
2nH (CH
2)
3si (OCH
3)
3(purchased from Debang Chemical New Material Co., Ltd., trade mark DB-792) and NH
2(CH
2)
2nH (CH
2)
3siCH
3(OCH
3)
2(purchased from Debang Chemical New Material Co., Ltd., trade mark DB-602) etc. the mixture that weight is mixed to get), cilicon oxide filler (the nano-silica powder of 2.1 weight parts, purchased from U.S. GE company, RNS-E, mean particle size 20nm), ((Silomer 8861 emulsions are (purchased from Richdale Special Chemicals Inc. for water-soluble silicon the third film-forming resin for the water-soluble film-forming resin of 6.5 weight parts (in solid), Rui De special chemical company, solid content is 43 % by weight))) and the water of 90 weight parts, under the stirring velocity of 1500 revs/min, be mixed to evenly, obtain the metal protection coating of the present embodiment.
Embodiment 5
By N-β-aminoethyl-γ-γ-aminopropylsilane coupling agent (NH of the promotor of the water-soluble silicate of 1 weight part (water glass, purchased from Baoding Run Feng Industrial Co., Ltd.), 1.7 weight parts (pyrrolidone and the thiocarbamide mixture that 1:1 obtains after mixing by weight), 4.5 weight parts
2(CH
2)
2nH (CH
2)
3si (OCH
2cH
3)
3(purchased from Debang Chemical New Material Co., Ltd., trade mark DB-793, NH
2(CH
2)
2nH (CH
2)
3si (OCH
3)
3(purchased from Debang Chemical New Material Co., Ltd., trade mark DB-792) and NH
2(CH
2)
2nH (CH
2)
3siCH
3(OCH
3)
2(purchased from Debang Chemical New Material Co., Ltd., trade mark DB-602) etc. the mixture that weight is mixed to get), cilicon oxide filler (the nano-silica powder of 0.3 weight part, purchased from U.S. GE company, RNS-E, mean particle size 20nm), ((Silomer 8861 emulsions are (purchased from Richdale Special Chemicals Inc. for water-soluble silicon the third film-forming resin for the water-soluble film-forming resin of 1.0 weight parts (in solid), Rui De special chemical company, solid content is 43 % by weight))) and the water of 15 weight parts, under the stirring velocity of 1500 revs/min, be mixed to evenly, obtain the metal protection coating of the present embodiment.
Embodiment 6
According to the method for embodiment 1, prepare metal protection coating, different, N-β-aminoethyl-γ-γ-aminopropylsilane coupling agent is NH
2(CH
2)
2nH (CH
2)
3si (OCH
2cH
3)
3(purchased from Debang Chemical New Material Co., Ltd., trade mark DB-793).
Embodiment 7
According to the method for embodiment 1, prepare metal protection coating, different, N-β-aminoethyl-γ-γ-aminopropylsilane 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).
Embodiment 8
According to the method for embodiment 1, prepare metal protection coating, 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 obtain after 1:1 mixes to add lubricating auxiliary agent, the water-based emulsion of dimethyl silicone oil is purchased from Nanjing Hua Tuo Chemical Co., Ltd., the trade mark is HTR-1, solid content is 30 % by weight, 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), wherein, with respect to the water-soluble silicate of 1 weight part, the consumption of lubricating auxiliary agent is 0.6 weight part.
Embodiment 9
According to the method for embodiment 8, prepare metal protection coating, different, do not add lubricating auxiliary agent.
Embodiment 10
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 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, and 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, and solid content is 48 % by weight, and the fusing point of oxidized polyethlene wax is 105-110 ℃, acid number is 14-21mgKOH/g), wherein, with respect to the water-soluble silicate of 1 weight part, the consumption of lubricating auxiliary agent is 0.5 weight part.
Embodiment 11
According to the method for embodiment 1, prepare metal protection coating, 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, 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 ℃), wherein, water-soluble silicate with respect to 1 weight part, the consumption of lubricating auxiliary agent is 0.7 weight part.
Embodiment 12
According to the method for embodiment 1, prepare metal protection coating, 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, 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 ℃), 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 metal protection coating that embodiment 1-12 and comparative example 1-4 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, warm air drying is 2 seconds at 90-110 ℃, the steel plate galvanized 1-16 after being processed.Wherein, coating amount makes the thickness of the coating on steel plate galvanized 1-16 be 0.8 micron.The thickness of coating is to use XRF(fluorescence spectrophotometer) numerical value measured of survey meter.
Preparation Example 2
Get the metal protection coating that embodiment 1-12 and comparative example 1-4 obtain and be coated on respectively Al-Zn coated steel (purchased from Pangang Group Panzhihua Steel Vanadium Co., Ltd., model DX51D+AZ, in aluminum-zinc alloy layer, contain zinc 42.5 % by weight, containing aluminium 52.3 % by weight) surface, at 90-110 ℃, warm air drying is 2 seconds, the Al-Zn coated steel 1-16 after being processed.Wherein, coating amount makes the thickness of the coating on Al-Zn coated steel 1-16 be 0.8 micron.The thickness of coating is to use XRF(fluorescence spectrophotometer) numerical value measured of survey meter.
Preparation Example 3
Get the metal protection coating that embodiment 1-12 and comparative example 1-4 obtain and be coated on respectively the zinc-magnesium steel plate of aluminizing (purchased from Pangang Group Panzhihua Steel Vanadium Co., Ltd., model DX53D+ZAM, aluminize in zinc-magnesium layer containing zinc 91 % by weight, containing aluminium 6 % by weight, containing magnesium 3 % by weight) surface, at 90-110 ℃, warm air drying is 2 seconds, the zinc-magnesium steel plate 1-16 that aluminizes after being processed.Wherein, coating amount make the to aluminize thickness of the coating on zinc-magnesium steel plate 1-16 is 0.8 micron.The thickness of coating is to use XRF(fluorescence spectrophotometer) numerical value measured of survey meter.
Test implementation example 1
By the requirement of regulation in GB/T 101251997, carry out neutral salt spray test, measure the corrosion resistance nature of steel plate galvanized 1-15, Al-Zn coated steel 1-16 and the zinc-magnesium steel plate 1-16 that aluminizes.It is qualified by " salt-fog test 96h, corrosion area < 20% ", to be considered as.
As follows, measure the water resistance of steel plate galvanized 1-16, Al-Zn coated steel 1-16 and the zinc-magnesium steel plate 1-16 that aluminizes.
Surface at steel plate galvanized 1-16, Al-Zn coated steel 1-16 and the zinc-magnesium steel plate 1-16 that aluminizes of horizontal positioned, drip the boiling water of approximately 2 milliliters, after seasoning in 24 hours, with 3M adhesive tape, will drip and locate to adhere to, to the spot counting under being stained with on adhesive tape, according to the counting of sticky lower spot on every square centimeter of adhesive tape, the quality of judgement rete water tolerance, spot under sticky is more, and water tolerance is poorer.
As follows, measure the thermotolerance of steel plate galvanized 1-16, Al-Zn coated steel 1-16 and the zinc-magnesium steel plate 1-16 that aluminizes.
Steel plate galvanized 1-16, Al-Zn coated steel 1-16 and the zinc-magnesium steel plate 1-16 that aluminizes are placed in hotblast stove, at 300 ℃, toast 20 minutes, then take out and observe coatingsurface morphology change, and adopt the Δ L(brightness variable of specimen surface before and after color difference meter test baking), the red green variable of Δ a(), Δ b(champac variable) value, and calculate Δ E(aberration)=(Δ L
2+ Δ a
2+ Δ b
2)
1/2.The less coating of Δ E has better thermotolerance.
As follows, measure the anti-finger printing of steel plate galvanized 1-16, Al-Zn coated steel 1-16 and the zinc-magnesium steel plate 1-16 that aluminizes.
Adopt the Δ L(brightness variable before and after color difference meter test steel plate galvanized 1-16, Al-Zn coated steel 1-16 and 0.5 gram/m of Vaseline of the zinc-magnesium steel plate 1-16 that aluminizes coating), the red green variable of Δ a(), Δ b(champac variable) value, and calculate Δ E(aberration)=(Δ L
2+ Δ a
2+ Δ b
2)
1/2, the less coating of Δ E has better anti-finger printing energy.
On M-2000 ring block type friction and wear tester, according to its specification sheets, measure the kinetic friction coefficient of the coating of test steel plate galvanized 1-16, Al-Zn coated steel 1-16 and the zinc-magnesium steel plate 1-16 that aluminizes.
Test result as above is as shown in table 1.
Table 1
Visible according to the data of table 1, solidity to corrosion, water tolerance, thermotolerance and the anti-finger printing of the protective film that metal protection coating provided by the invention forms are all 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 N-β-aminoethyl-γ-γ-aminopropylsilane coupling agent is 1.4-1.8 weight part, 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 metal protection coating formation, water tolerance, thermotolerance and anti-finger printing.And, visible according to the data of table 1, in the situation that preferred described water-soluble silicon the third film-forming resin is Silomer 8861 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 metal protection coating forms.In addition according to the data of table 1, at preferred described N-β-aminoethyl-γ-γ-aminopropylsilane coupling agent, be NH,
2(CH
2)
2nH (CH
2)
3si (OCH
2cH
3)
3, NH
2(CH
2)
2nH (CH
2)
3si (OCH
3)
3and NH
2(CH
2)
2nH (CH
2)
3siCH
3(OCH
3)
2by 1:(0.5-2): in the situation of the mixture that weight ratio (0.5-2) is mixed to get, can further improve solidity to corrosion, water tolerance, thermotolerance and the anti-finger printing of the protective film of described metal protection coating formation.
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 metal protection coating, this metal protection coating obtains after being mixed by a kind of raw mixture, described raw mixture contains water-soluble silicate, cilicon oxide filler, promotor, water-soluble film-forming resin, N-β-aminoethyl-γ-γ-aminopropylsilane coupling agent and water; Described promotor is contained the first promotor and/or the second promotor, and described the first promotor is at least one in pyrrolidone, N-Methyl pyrrolidone and N-ethyl pyrrolidone, and described the second promotor is thiocarbamide and/or urea; Described N-β-aminoethyl-γ-γ-aminopropylsilane coupling agent is NH
2(CH
2)
2nH (CH
2)
3si (OCH
2cH
3)
3, NH
2(CH
2)
2nH (CH
2)
3si (OCH
3)
3and NH
2(CH
2)
2nH (CH
2)
3siCH
3(OCH
3)
2in at least one.
2. metal protection coating according to claim 1, wherein, described water-soluble silicate with respect to 1 weight part, the content of described promotor is 0.2-1.8 weight part, the consumption of described N-β-aminoethyl-γ-γ-aminopropylsilane coupling agent is 0.5-4.5 weight part, and 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, and the consumption of water is 10-100 weight part.
3. metal protection coating according to claim 2, wherein, 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 N-β-aminoethyl-γ-γ-aminopropylsilane coupling agent is 1.4-1.8 weight part, and 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, and the consumption of water is 25-40 weight part.
4. according to the metal protection coating described in any one in claim 1-3, wherein, described N-β-aminoethyl-γ-γ-aminopropylsilane coupling agent is NH
2(CH
2)
2nH (CH
2)
3si (OCH
2cH
3)
3, NH
2(CH
2)
2nH (CH
2)
3si (OCH
3)
3and NH
2(CH
2)
2nH (CH
2)
3siCH
3(OCH
3)
2by weight 1:(0.5-2): the mixture (0.5-2) being mixed to get.
5. according to the metal protection coating described in any one in claim 1-3, wherein, described cilicon oxide filler is nano-silica powder and/or silicon sol.
6. according to the metal protection coating described in any one in claim 1-3, 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 Silomer 8861 emulsions.
7. according to the metal protection coating described in any one in claim 1-3, wherein, described raw mixture also contains 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 content of described lubricating auxiliary agent is 0.2-1.8 weight part.
8. the purposes of the metal protection coating described in any one in preparing metallic substance in claim 1-7.
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 the metal protection coating described in any one in claim 1-7.
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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Cited By (1)
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|---|---|---|---|---|
| CN109423081A (en) * | 2017-06-23 | 2019-03-05 | 镇江瑞德新材料科技研发有限公司 | A kind of manufacturing method and application thereof of metal protection coating |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003201578A (en) * | 2002-01-11 | 2003-07-18 | Nippon Parkerizing Co Ltd | Chromium-free surface-treated aluminum-zinc based alloy plated steel sheet |
| CN1730570A (en) * | 2005-08-02 | 2006-02-08 | 陈国军 | High temperature energy-saving corrosion-resisting paint , preparation and usage |
-
2012
- 2012-06-29 CN CN201210220576.XA patent/CN103509441B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003201578A (en) * | 2002-01-11 | 2003-07-18 | Nippon Parkerizing Co Ltd | Chromium-free surface-treated aluminum-zinc based alloy plated steel sheet |
| CN1730570A (en) * | 2005-08-02 | 2006-02-08 | 陈国军 | High temperature energy-saving corrosion-resisting paint , preparation and usage |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109423081A (en) * | 2017-06-23 | 2019-03-05 | 镇江瑞德新材料科技研发有限公司 | A kind of manufacturing method and application thereof of metal protection coating |
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