CN103509390B - A kind of metal protection coating and uses thereof and hot-dip metal plated material - Google Patents
A kind of metal protection coating and uses thereof and hot-dip metal plated material Download PDFInfo
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- CN103509390B CN103509390B CN201210220535.0A CN201210220535A CN103509390B CN 103509390 B CN103509390 B CN 103509390B CN 201210220535 A CN201210220535 A CN 201210220535A CN 103509390 B CN103509390 B CN 103509390B
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Abstract
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, water-soluble film-forming resin, N-β-aminoethyl-γ-γ-aminopropylsilane coupling agent and water.Present invention also offers above-mentioned metal protection coating and prepare the purposes in metallic substance.Present invention also offers 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, and described coating is the cured product of metal protection coating as above.The solidity to corrosion of the protective film that metal protection coating provided by the invention is formed, water tolerance, thermotolerance and anti-finger printing are all very excellent.
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 the hot-dip metal plated material of one.
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 at the surface application layer of metal protective coating of hot-dip metal plated material to form protective film.Thus the performance of metal protection coating is very important for the rust protection of hot-dip metal plated material.
Such as, 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 containing 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 experiment proves, the solidity to corrosion of protective film that this metal protection coating is formed, water tolerance, thermotolerance and anti-finger printing are still poor.
Summary of the invention
The object of the invention is the defect that the solidity to corrosion of the protective film overcoming the formation of existing metal protection coating, water tolerance, thermotolerance and anti-finger printing are poor, a kind of metal protection coating that can form the good protective film of solidity to corrosion, water tolerance, thermotolerance and anti-finger printing is provided.
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, water-soluble film-forming resin, N-β-aminoethyl-γ-γ-aminopropylsilane coupling agent and water; 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.
Present invention also offers above-mentioned metal protection coating and prepare the purposes in metallic substance.
Present invention also offers 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, the solidity to corrosion of the protective film that metal protection coating provided by the invention is formed, water tolerance, thermotolerance and anti-finger printing are all very excellent.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of 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, water-soluble film-forming resin, N-β-aminoethyl-γ-γ-aminopropylsilane coupling agent and water; 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-aminopropyltriethoxy dimethoxysilane), can be used as silane coupling agent, the commercially available commodity shown in 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 obtain after described raw mixture mixes, and is comparatively stable and homogeneous liquid.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 specially required, directly each component in described raw mixture can be carried out mixing simultaneously, in batches or step by step, as long as uniform stable phase can be obtained, make mixing more even preferably by stirring.
According to metal protection coating provided by the invention, wherein, relative 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, relative 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, relative 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, relative 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 added in addition, 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 to improve the performance of described metal protection coating further, 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 the weight ratio of (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 the various fillers based on silicon oxide, and such as, 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 for various water miscible and can be used in the modification of film forming or unmodified resin, described resin can use with suitable object form, such as water-soluble emulsion, at least one in water-soluble solution and water-soluble solid, the not special requirement of the present invention, as long as the film forming of can be used in, such as, described water-soluble film-forming resin can be the water-soluble polyester film-forming resin (water-soluble film-forming resin namely obtained by polyalcohols monomer and polynary acids monomer polymerization, such as purchased from Guangzhou Lapo Fine Chemicals Co., Ltd., the vibrin of trade mark CB2200), the water-soluble phenylpropyl alcohol film-forming resin (water-soluble film-forming resin namely obtained by styrene monomer and vinylformic acid (ester) class monomer polymerization, such as 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 namely obtained by the monomer polymerization containing epoxy group(ing), such as purchased from Dongguan City Heima Chemical Co., Ltd., the trade mark is the epoxy resin of BH620), aqurous ployurethane film-forming resin (the water-soluble film-forming resin namely obtained by multicomponent isocyanate class monomer and multi-hydroxy compounds monomer polymerization, such as purchased from Jinjiang, Fujian Province Jian Hua company, the urethane resin of the trade mark 812), the water-soluble silicon third film-forming resin (water-soluble film-forming resin namely obtained by silicone based monomer and vinylformic acid (ester) class monomer polymerization, make the country prosperous paint company TC-05 type organosilicon crylic acid latex in such as Qingdao, solid content is 48 % by weight), water-soluble acrylic film-forming resin (the water-soluble film-forming resin namely obtained by vinylformic acid (ester) class monomer polymerization, the trade mark such as purchased from Guangzhou Ou Peng chemical industry is the acrylic resin of A-3418) and the water-soluble fluorine carbon film-forming resin (water-soluble film-forming resin namely obtained by fluorinated monomer polymerization, such as 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 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 third film-forming resin is Silomer8861 emulsion (purchased from RichdaleSpecialChemicalsInc., Rui De special chemical company).
According to metal protection coating provided by the invention, wherein, in order to improve the lubricity of the protective film of formation further, under preferable case, metal protection coating of the present invention is also containing lubricating auxiliary agent, and described lubricating auxiliary agent is one or more in the water-based emulsion of dimethyl silicone oil, polyether-modified polysiloxane, the water-based emulsion of polyethylene wax and the water-based emulsion of oxidized polyethlene wax.
More preferably, relative 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 for preparing metal protection coating provided by the invention, and its consumption refers to the numerical value obtained after the gross weight of water-based emulsion is multiplied by 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 preparing described dimethyl silicone oil 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, is 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.Preferred described polyether-modified polysiloxane is viscosity is 100-10000mPas, is preferably 500-8000mPas, is more preferably 1000-6000mPas, is further preferably the water-soluble dimethyl silicone oil of 2000-5000mPas.
It should be noted that, when not doing contrary explanation in the present invention, described viscosity refers to the apparent viscosity numerical value recorded at 25 DEG C.
Wherein, the water-based emulsion of described polyethylene wax can be the water-based emulsion conventionally will obtained after polyethylene wax emulsification, and 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 for preparing metal protection coating provided by the invention, and its consumption refers to the numerical value obtained after the gross weight of water-based emulsion is multiplied by its solid content.
Wherein, the fusing point of the polyethylene wax in the water-based emulsion of described polyethylene wax can be 90-130 DEG C, is preferably 100-120 DEG C, is more preferably 105-115 DEG C.
Wherein, the water-based emulsion of described oxidized polyethlene wax can be the water-based emulsion conventionally will obtained after oxidized polyethlene wax emulsification, and 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 for preparing metal protection coating provided by the invention, and its consumption refers to the numerical value obtained after the gross weight of water-based emulsion is multiplied by 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 DEG C, is preferably 90-115 DEG C, is more preferably 100-110 DEG C.
It should be noted that, when not doing contrary explanation in the present invention, the fusing point of polyethylene wax and oxidized polyethlene wax refers to the numerical value measured according to the 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 measured according to GB/T264-83 petroleum product acid value measuring method.
Except containing except mentioned component, metal protection coating of the present invention can also contain other various component not affecting metal protection coating property, as one or more in dyestuff, pigment, dispersion agent and defoamer.With the gross weight of this metal protection coating for benchmark, the content of other component is no more than 20 % by weight, preferably more than 10 % by weight.Described defoamer can be various defoamer well known in the art, such as, in polyethers defoamer, higher alcohols defoamer and silicon defoamer etc. one or more.More particularly, described defoamer can one or more for being purchased in the SD-401 of such as limited liability company of Dongying dan large Creative Science and Technology Co. Ltd series defoamer.Under preferable case, with the total amount of described metal protection coating for benchmark, the content of described defoamer is 0.01-0.05 % by weight.
Metal protection coating of the present invention can directly use without the need to dilution.
Present invention also offers above-mentioned metal protection coating and prepare the purposes in metallic substance.Above-mentioned metal protection coating can 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 for the metal base containing 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 for the metal base containing 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 for the metal base containing 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 general 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 that hot-dip metal plated base material adheres to described coating can comprise and is attached on the surface of hot-dip metal plated base material by described metal protection coating, then dry, dry temperature can be 60-120 DEG C, be preferably 90-110 DEG C, 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, the method for described drying can be one or more in warm air drying, induction heating and infrared radiation heating.
In the present invention, when not doing contrary explanation, the volume of all liquid and solid all refers to 20 DEG C, the volume of 1 standard atmosphere pressure.
Below will be explained in further detail the present invention by embodiment.In following examples and comparative example, simultaneously each raw material of metal protection coating substantially adds in container.
Embodiment 1
By the water-soluble silicate (water glass, purchased from Baoding Run Feng Industrial Co., Ltd.) of 1 weight part, the N-β-aminoethyl-γ-γ-aminopropylsilane coupling agent (NH of 1.6 weight parts
2(CH
2)
2nH (CH
2)
3si (OCH
2cH
3)
3(purchased from Debang Chemical New Material Co., Ltd., the 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 is mixed to get of weight), cilicon oxide filler (the nano-silica powder of 0.72 weight part, purchased from American GE company, RNS-E, mean particle size 20nm), ((Silomer8861 emulsion is (purchased from RichdaleSpecialChemicalsInc. for water-soluble silicon 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, be mixed to evenly under the stirring velocity of 1500 revs/min, obtain the metal protection coating of the present embodiment.
Comparative example 1
Metal protection coating is prepared according to the method for embodiment 1, unlike, replace N-β-aminoethyl-γ-γ-aminopropylsilane coupling agent with aminopropyl triethoxysilane (purchased from Hubei Li Meida fluosilicic Science and Technology Ltd., trade mark LMD-1100).
Comparative example 2
Metal protection coating is prepared according to the method for embodiment 1, unlike, do not add water-soluble silicate.
Comparative example 3
Metal protection coating is prepared according to the method for embodiment 1, unlike, do not add cilicon oxide filler.
Embodiment 2
By the water-soluble silicate (potassium silicate, purchased from Baoding Run Feng Industrial Co., Ltd.) of 1 weight part, the 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., the 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 that is 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 American GE company, RNS-E, mean particle size 20nm), ((Silomer8861 emulsion is (purchased from RichdaleSpecialChemicalsInc. for water-soluble silicon 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, be mixed to evenly under the stirring velocity of 1500 revs/min, obtain the metal protection coating of the present embodiment.
Embodiment 3
By the water-soluble silicate (water glass, purchased from Baoding Run Feng Industrial Co., Ltd.) of 1 weight part, the 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., the 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 that is mixed to get according to the weight ratio of 1:2:0.5), cilicon oxide filler (the silicon sol of 30 % by weight of 0.85 weight part, usage quantity is in solid), ((Silomer8861 emulsion is (purchased from RichdaleSpecialChemicalsInc. for water-soluble silicon 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, be mixed to evenly under the stirring velocity of 1500 revs/min, obtain the metal protection coating of the present embodiment.
Embodiment 4
By the water-soluble silicate (water glass, purchased from Baoding Run Feng Industrial Co., Ltd.) of 1 weight part, the N-β-aminoethyl-γ-γ-aminopropylsilane coupling agent (NH of 0.6 weight part
2(CH
2)
2nH (CH
2)
3si (OCH
2cH
3)
3(purchased from Debang Chemical New Material Co., Ltd., the 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 is mixed to get of weight), cilicon oxide filler (the nano-silica powder of 2.1 weight parts, purchased from American GE company, RNS-E, mean particle size 20nm), ((Silomer8861 emulsion is (purchased from RichdaleSpecialChemicalsInc. for water-soluble silicon 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, be mixed to evenly under the stirring velocity of 1500 revs/min, obtain the metal protection coating of the present embodiment.
Embodiment 5
By the water-soluble silicate (water glass, purchased from Baoding Run Feng Industrial Co., Ltd.) of 1 weight part, the N-β-aminoethyl-γ-γ-aminopropylsilane coupling agent (NH of 4.5 weight parts
2(CH
2)
2nH (CH
2)
3si (OCH
2cH
3)
3(purchased from Debang Chemical New Material Co., Ltd., the 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 is mixed to get of weight), cilicon oxide filler (the nano-silica powder of 0.3 weight part, purchased from American GE company, RNS-E, mean particle size 20nm), ((Silomer8861 emulsion is (purchased from RichdaleSpecialChemicalsInc. for water-soluble silicon 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, be mixed to evenly under the stirring velocity of 1500 revs/min, obtain the metal protection coating of the present embodiment.
Embodiment 6
Metal protection coating is prepared according to the method for embodiment 1, unlike, 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
Metal protection coating is prepared according to the method for embodiment 1, unlike, 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
Metal protection coating is prepared according to the method for embodiment 1, unlike, (make the country prosperous paint company TC-05 type organosilicon crylic acid latex in Qingdao to use water-soluble silicon third film-forming resin, 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 mixing 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, be obtain after the dimethyl silicone oil emulsification of 25000mPas by the apparent viscosity at 25 DEG C, polyether-modified polysiloxane is purchased from dyeing and finishing auxiliaries for textile Co., Ltd., Factory of Dongguan Acer, and the apparent viscosity at 25 DEG C is 3000mPas), wherein, relative to the water-soluble silicate of 1 weight part, the consumption of lubricating auxiliary agent is 0.6 weight part.
Embodiment 9
Metal protection coating is prepared according to the method for embodiment 8, unlike, 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 mixing 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 DEG C; 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 DEG C, acid number is 14-21mgKOH/g), wherein, relative to the water-soluble silicate of 1 weight part, the consumption of lubricating auxiliary agent is 0.5 weight part.
Embodiment 11
Metal protection coating is prepared according to the method for embodiment 1, unlike, 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, be obtain after the dimethyl silicone oil emulsification of 1500mPas by the apparent viscosity at 25 DEG C), wherein, relative to the water-soluble silicate of 1 weight part, the consumption of lubricating auxiliary agent is 0.7 weight part.
Embodiment 12
Metal protection coating is prepared according to the method for embodiment 1, unlike, 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, be obtain after the dimethyl silicone oil emulsification of 1500mPas by the apparent viscosity at 25 DEG C), wherein, relative to the water-soluble silicate of 1 weight part, the consumption of lubricating auxiliary agent is 0.7 weight part.
Preparation embodiment 1
The metal protection coating that Example 1-12 and comparative example 1-3 obtains is coated on steel plate galvanized respectively (purchased from Pangang Group Panzhihua Steel Vanadium Co., Ltd., model DX54D, containing zinc 95 % by weight in zinc coating) surface, warm air drying 2 seconds at 90-110 DEG C, obtains the steel plate galvanized 1-15 after processing.Wherein, coating amount makes the thickness of the coating on steel plate galvanized 1-15 be 0.8 micron.The thickness of coating uses XRF(fluorescence spectrophotometer) survey meter measure numerical value.
Preparation embodiment 2
The metal protection coating that Example 1-12 and comparative example 1-3 obtains is coated on Al-Zn coated steel respectively (purchased from Pangang Group Panzhihua Steel Vanadium Co., Ltd., model DX51D+AZ, containing zinc 42.5 % by weight in zinc layers of aluminizing, containing aluminium 52.3 % by weight) surface, warm air drying 2 seconds at 90-110 DEG C, obtains the Al-Zn coated steel 1-15 after processing.Wherein, coating amount makes the thickness of the coating on Al-Zn coated steel 1-15 be 0.8 micron.The thickness of coating uses XRF(fluorescence spectrophotometer) survey meter measure numerical value.
Preparation embodiment 3
The metal protection coating that Example 1-12 and comparative example 1-3 obtains is coated on zinc-magnesium steel plate of aluminizing respectively (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, warm air drying 2 seconds at 90-110 DEG C, obtains the zinc-magnesium steel plate 1-15 that aluminizes after processing.Wherein, coating amount makes the thickness of the coating of aluminizing on zinc-magnesium steel plate 1-15 be 0.8 micron.The thickness of coating uses XRF(fluorescence spectrophotometer) survey meter measure numerical value.
Testing example 1
By the requirement specified in GB/T101251997, carry out neutral salt spray test, measure the corrosion resistance nature of steel plate galvanized 1-15, Al-Zn coated steel 1-15 and the zinc-magnesium steel plate 1-15 that aluminizes.It is qualified to be considered as by " salt-fog test 96h, corrosion area < 20% ".
As follows, the water resistance of steel plate galvanized 1-15, Al-Zn coated steel 1-15 and the zinc-magnesium steel plate 1-15 that aluminizes is measured.
On steel plate galvanized 1-15, the Al-Zn coated steel 1-15 of horizontal positioned and the surface of the zinc-magnesium steel plate 1-15 that aluminizes, drip the boiling water of about 2 milliliters, after seasoning in 24 hours, to drip with 3M adhesive tape and locate to adhere to, to the spot count under adhesive tape is stained with, according to the counting of lower spot sticky on every square centimeter of adhesive tape, judge the quality of rete water tolerance, spot under sticky is more, and water tolerance is poorer.
As follows, the thermotolerance of steel plate galvanized 1-15, Al-Zn coated steel 1-15 and the zinc-magnesium steel plate 1-15 that aluminizes is measured.
Steel plate galvanized 1-15, Al-Zn coated steel 1-15 and the zinc-magnesium steel plate 1-15 that aluminizes are placed in hotblast stove, toast 20 minutes at 300 DEG C, then take out and observe coating morphology change, and adopt color difference meter to test the Δ L(lightness variable of specimen surface before and after 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.Namely the less coating of Δ E has more excellent thermotolerance.
As follows, the anti-finger printing of steel plate galvanized 1-15, Al-Zn coated steel 1-15 and the zinc-magnesium steel plate 1-15 that aluminizes is measured.
Adopt color difference meter test steel plate galvanized 1-15, Al-Zn coated steel 1-15 and the zinc-magnesium steel plate 1-15 that aluminizes apply Δ L(lightness variable before and after 0.5 gram/m of Vaseline), 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, namely the less coating of Δ E has more excellent anti-finger printing energy.
On M-2000 ring block type friction and wear tester, according to the kinetic friction coefficient of the coating of its specification sheets mensuration test steel plate galvanized 1-15, Al-Zn coated steel 1-15 and the zinc-magnesium steel plate 1-15 that aluminizes.
Test result as above is as shown in table 1.
Table 1
Visible according to the data of table 1, the solidity to corrosion of the protective film that metal protection coating provided by the invention is formed, water tolerance, thermotolerance and anti-finger printing are all very excellent.And, visible according to the data of table 1, at the preferred described water-soluble silicate relative to 1 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, when the consumption of water is 25-40 weight part, the solidity to corrosion of the protective film that described metal protection coating is formed, water tolerance, thermotolerance and anti-finger printing can be improved further.And, visible according to the data of table 1, when preferred described water-soluble silicon third film-forming resin is Silomer8861 emulsion, or when preferred described raw mixture also contains lubricating auxiliary agent, the oilness of the protective film that described metal protection coating is formed can be improved further.In addition, according to the data of table 1, be NH at preferred described N-β-aminoethyl-γ-γ-aminopropylsilane coupling agent
2(CH
2)
2nH (CH
2)
3si (OCH
2cH
3)
3, NH
2(CH
2)
2nH (CH
2)
3i (OCH
3)
3and NH
2(CH
2)
2nH (CH
2)
3siCH
3(OCH
3)
2by 1:(0.5-2): when the mixture that the weight ratio of (0.5-2) is mixed to get, the solidity to corrosion of the protective film that described metal protection coating is formed, water tolerance, thermotolerance and anti-finger printing can be improved further.
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 characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, 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 (7)
1. a 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, water-soluble film-forming resin, N-β-aminoethyl-γ-γ-aminopropylsilane coupling agent, lubricating auxiliary agent and water, 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 the mixture that the weight ratio of 1:0.5-2:0.5-2 is mixed to get, described lubricating auxiliary agent is one or more in the water-based emulsion of dimethyl silicone oil, polyether-modified polysiloxane, the water-based emulsion of polyethylene wax and the water-based emulsion of oxidized polyethlene wax, the solid content of the water-based emulsion of described dimethyl silicone oil is 10-90 % by weight, and the dimethyl-silicon oil viscosity in the water-based emulsion of described dimethyl silicone oil is 500-50000mPas, the viscosity of described polyether-modified polysiloxane is 100-10000mPas, the solid content of the water-based emulsion of described polyethylene wax is 30-60 % by weight, and the fusing point of the polyethylene wax in the water-based emulsion of described polyethylene wax is 90-130 DEG C, the solid content of the water-based emulsion of described oxidized polyethlene wax is 30-60 % by weight, the fusing point of the oxidized polyethlene wax in the water-based emulsion of described oxidized polyethlene wax is 80-120 DEG C, the acid number of oxidized polyethlene wax is 5-60mgKOH/g, relative to the described water-soluble silicate of 1 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 25-40 weight part, the content of described lubricating auxiliary agent is 0.2-1.8 weight part.
2. metal protection coating according to claim 1, wherein, described cilicon oxide filler is nano-silica powder and/or silicon sol.
3. metal protection coating according to claim 1, 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 third film-forming resin, water-soluble acrylic film-forming resin and water-soluble fluorine carbon film-forming resin.
4. metal protection coating according to claim 3, wherein, described water-soluble silicon third film-forming resin is Silomer8861 emulsion.
5. the purposes in metallic substance prepared by the metal protection coating in claim 1-4 described in any one.
6. 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 in claim 1-4 described in any one.
7. hot-dip metal plated material according to claim 6, wherein, the thickness of described coating is 0.1-1 micron.
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| CN201210220535.0A CN103509390B (en) | 2012-06-29 | 2012-06-29 | A kind of metal protection coating and uses thereof and hot-dip metal plated material |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1172135A (en) * | 1996-05-20 | 1998-02-04 | 金属涂层国际公司 | Water-reducible coating composition for providing corrosion protection |
| CN101486869A (en) * | 2009-02-18 | 2009-07-22 | 南京大学 | Preparation of high performance metal protection nano coating |
| CN101701336A (en) * | 2009-11-26 | 2010-05-05 | 芜湖市瑞杰环保材料科技有限公司 | Environment-friendly metal surface treating agent and using method thereof |
| CN101891998A (en) * | 2009-05-18 | 2010-11-24 | 攀钢集团钢铁钒钛股份有限公司 | Paint composition and galvanized passivated material |
-
2012
- 2012-06-29 CN CN201210220535.0A patent/CN103509390B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1172135A (en) * | 1996-05-20 | 1998-02-04 | 金属涂层国际公司 | Water-reducible coating composition for providing corrosion protection |
| CN101486869A (en) * | 2009-02-18 | 2009-07-22 | 南京大学 | Preparation of high performance metal protection nano coating |
| CN101891998A (en) * | 2009-05-18 | 2010-11-24 | 攀钢集团钢铁钒钛股份有限公司 | Paint composition and galvanized passivated material |
| CN101701336A (en) * | 2009-11-26 | 2010-05-05 | 芜湖市瑞杰环保材料科技有限公司 | Environment-friendly metal surface treating agent and using method thereof |
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