CN104059409B - A kind of surface conversion layer forming agent and its production and use and hot-dip metal plated material - Google Patents
A kind of surface conversion layer forming agent and its production and use and hot-dip metal plated material Download PDFInfo
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- CN104059409B CN104059409B CN201310159989.6A CN201310159989A CN104059409B CN 104059409 B CN104059409 B CN 104059409B CN 201310159989 A CN201310159989 A CN 201310159989A CN 104059409 B CN104059409 B CN 104059409B
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Abstract
The invention provides a kind of preparation method of surface conversion layer forming agent, the method comprises and water, silane coupling agent, water-soluble silicate, cilicon oxide filler and water-soluble film-forming resin being mixed successively.Present invention also offers the surface conversion layer forming agent for preparing according to preparation method as above and above-mentioned surface conversion layer forming agent is preparing 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 surface conversion layer forming agent as above.The solidity to corrosion of the protective film that surface conversion layer forming agent provided by the invention is formed is very excellent.In addition, the storage endurance of surface conversion layer forming agent provided by the invention is very excellent, at room temperature can store 180 days and the change of obvious proterties and degradation do not occur after preparation completes.
Description
Technical field
The present invention relates to metal protection field, particularly, the purposes of the preparation method relating to a kind of surface conversion layer forming agent, the surface conversion layer forming agent obtained by this preparation method, this surface conversion layer forming agent and 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 in the surface application layer of surface conversion coating forming agent of hot-dip metal plated material to form protective film.Thus the performance of surface conversion layer forming agent is very important for the rust protection of hot-dip metal plated material.
Such as, CN101608306A discloses a kind of passivating solution, also a kind of surface conversion layer forming agent is belonged to, 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, wherein, described water soluble organic substance is the mixture of alcohol and organic carboxyl acid.
But experiment proves, the solidity to corrosion of the protective film that this surface conversion layer forming agent is formed is still poor.
Summary of the invention
The object of the invention is to overcome the defect that the solidity to corrosion of the protective film that existing surface conversion layer forming agent is formed is poor, a kind of surface conversion layer forming agent that can form the good protective film of solidity to corrosion is provided.
To achieve these goals, the invention provides a kind of preparation method of surface conversion layer forming agent, the method comprises and water, silane coupling agent, water-soluble silicate, cilicon oxide filler and water-soluble film-forming resin being mixed successively; Described silane coupling agent contains the first silane coupling agent and the second silane coupling agent; Wherein said 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 CH independently of one another
2(O) CHCH
2o (CH
2)
3-or
(CH
2)
2; Described second silane coupling agent is CH
2=C (CH
3) COO (CH
2)
3si (OCH
3)
3, CH
2=C (CH
3) COO (CH
2)
3si (OC
2h
5)
3, CH
2=C (CH
3) COO (CH
2)
3siCH
3(OCH
3)
2and CH
2=C (CH
3) COO (CH
2)
3siCH
3(OC
2h
5)
2in at least one.
Present invention also offers the surface conversion layer forming agent prepared according to preparation method as above.
Present invention also offers above-mentioned surface conversion layer forming agent 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 surface conversion layer forming agent as above.
By technique scheme, the solidity to corrosion of the protective film that surface conversion layer forming agent provided by the invention is formed is very excellent.In addition, the storage endurance of surface conversion layer forming agent provided by the invention is very excellent, at room temperature can store 180 days and the change of obvious proterties and degradation do not occur after preparation completes.
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.
The invention provides a kind of preparation method of surface conversion layer forming agent, the method comprises and water, silane coupling agent, water-soluble silicate, cilicon oxide filler and water-soluble film-forming resin being mixed successively; Described silane coupling agent contains the first silane coupling agent and the second silane coupling agent; Wherein said 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 CH independently of one another
2(O) CHCH
2o (CH
2)
3-or
(CH
2)
2-; Described second silane coupling agent is CH
2=C (CH
3) COO (CH
2)
3si (OCH
3)
3, CH
2=C (CH
3) COO (CH
2)
3si (OC
2h
5)
3, CH
2=C (CH
3) COO (CH
2)
3siCH
3(OCH
3)
2and CH
2=C (CH
3) COO (CH
2)
3siCH
3(OC
2h
5)
2in at least one.
Wherein, in detail, the method comprises: water and described silane coupling agent mix by (1), obtain uniform liquid A; (2) described uniform liquid A and water-soluble silicate are mixed, obtain uniform liquid B; (3) described uniform liquid B and cilicon oxide filler are mixed, obtain uniform liquid C; (4) described uniform liquid C is mixed with water-soluble film-forming resin, obtain uniform liquid D.Wherein, there is no particular limitation for the method mixed, as long as can obtain uniform stable phase, makes mixing more even preferably by stirring.
According to the preparation method of surface conversion layer forming agent provided by the invention, wherein, relative to the described water-soluble silicate of 1 weight part, the consumption of described silane 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 weight ratio of described first silane coupling agent and described second silane coupling agent is 3-5:1, is preferably 3.7-4.3:1.
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 the preparation method of surface conversion layer forming agent provided by the invention, wherein, under preferable case, described first silane coupling agent is CH
2(O) CHCH
2o (CH
2)
3si (OCH
3)
3, CH
2(O) CHCH
2o (CH
2)
3si (OC
2h
5)
3, CH
2(O) CHCH
2o (CH
2)
3siCH
3(OCH
3)
2, CH
2(O) CHCH
2o (CH
2)
3siCH
3(OC
2h
5)
2,
(CH
2)
2si (OCH
3)
3with
(CH
2)
2si (OC
2h
5)
3in at least one.Wherein, CH
2(O) CHCH
2o (CH
2)
3si (OCH
3)
3(being called γ-glycydoxy Trimethoxy silane), CH
2(O) CHCH
2o (CH
2)
3si (OC
2h
5)
3(being called γ-glycydoxy triethoxyl silane), CH
2(O) CHCH
2o (CH
2)
3siCH
3(OCH
3)
2(being called γ-glycydoxy methyl dimethoxysilane), CH
2(O) CHCH
2o (CH
2)
3siCH
3(OC
2h
5)
2(being called γ-glycydoxy methyldiethoxysilane),
(CH
2)
2si (OCH
3)
3(being called 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane) and
(CH
2)
2si (OC
2h
5)
3(be called 2-(3,4-epoxycyclohexyl) ethyl triethoxysilane) can the first silane coupling agent be used as, 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, and such as, the trade mark purchased from Debang Chemical New Material Co., Ltd. is the commercially available product of DB-560, DB-563, DB-561, DB-562, DB-186 and DB-1770.Wherein, more preferably described first silane coupling agent is CH
2(O) CHCH
2o (CH
2)
3si (OCH
3)
3.
Described second silane coupling agent is CH
2=C (CH
3) COO (CH
2)
3si (OCH
3)
3, CH
2=C (CH
3) COO (CH
2)
3si (OC
2h
5)
3, CH
2=C (CH
3) COO (CH
2)
3siCH
3(OCH
3)
2and CH
2=C (CH
3) COO (CH
2)
3siCH
3(OC
2h
5)
2in at least one.Wherein, CH
2=C (CH
3) COO (CH
2)
3si (OCH
3)
3(being called γ-methacryloxypropyl trimethoxy silane), CH
2=C (CH
3) COO (CH
2)
3si (OC
2h
5)
3(being called γ-methacryloxypropyl), CH
2=C (CH
3) COO (CH
2)
3siCH
3(OCH
3)
2(being called γ-methacryloyloxypropyl methyl dimethoxysilane) and CH
2=C (CH
3) COO (CH
2)
3siCH
3(OC
2h
5)
2(being called γ-methacryloyloxypropyl methyl diethoxy silane) can be used as the second 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, the trade mark such as purchased from Debang Chemical New Material Co., Ltd. is the commercially available product of DB-570, DB-571 and DB-572, and is the commercially available product of Luer-1512 purchased from the trade mark of Rule, Shanghai Chemical trade company limited.Wherein, preferably described second silane coupling agent is CH
2=C (CH
3) COO (CH
2)
3si (OCH
3)
3.
According to the preparation method of surface conversion layer forming agent provided by the invention, 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.Further, the consumption of described water-soluble silicate calculates with the gauge of anhydrous silicate.
According to the preparation method of surface conversion layer forming agent provided by the invention, wherein, described cilicon oxide filler does not have special requirement, can be the various fillers based on silicon oxide, such as, 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, be more preferably 5-30nm, such as, 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 can be used, 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 with the Weight computation of silicon oxide itself, the consumption of such as nano silicon dioxide sol calculates with the gauge of the silicon-dioxide in colloidal sol, the numerical evaluation obtained after being namely multiplied by its dioxide-containing silica percentage ratio (weight) with the weight of nano silicon dioxide sol.
According to the preparation method of surface conversion layer forming agent 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 the preparation method of surface conversion layer forming agent provided by the invention, wherein, in order to improve the lubricity of the protective film of formation further, under preferable case, this preparation method also comprises: the material after water and silane coupling agent being mixed mixes with 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 surface conversion layer forming agent 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 surface conversion layer forming agent 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 surface conversion layer forming agent 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.
Present invention also offers the surface conversion layer forming agent prepared according to preparation method as above.Wherein, obtain in preparation method as above add water-soluble film-forming resin and material (that is, the uniform liquid D obtained) after mixing namely can use as surface conversion layer forming agent of the present invention.
In addition, surface conversion layer forming agent of the present invention can also contain other various component not affecting surface conversion layer forming agent character, as one or more in dyestuff, pigment, dispersion agent and defoamer.With the gross weight of this surface conversion layer forming agent 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 surface conversion layer forming agent for benchmark, the content of described defoamer is 0.01-0.05 % by weight.
Correspondingly, the preparation method of surface conversion layer forming agent provided by the invention can also comprise add other various do not affect surface conversion layer forming agent character component and the step mixed.These other various component not affecting surface conversion layer forming agent character can add after adding water-soluble film-forming resin again.
Surface conversion layer forming agent of the present invention can directly use without the need to dilution.
Present invention also offers above-mentioned surface conversion layer forming agent and prepare the purposes in metallic substance.Above-mentioned surface conversion layer forming agent 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, wherein, described coating is the cured product of surface conversion layer forming agent 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 metal base 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.Wherein, the thickness of coating uses XRF(fluorescence spectrophotometer) survey meter measure numerical value.
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 surface conversion layer forming agent, 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 surface conversion layer forming agent 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.
Embodiment 1
Be mixed under the stirring velocity of 1500 revs/min evenly by the silane coupling agent (being made up of the first silane coupling agent and the second silane coupling agent) of the water of 28 weight parts and 1.6 weight parts, obtain uniform liquid A, wherein, the first silane coupling agent is CH
2(O) CHCH
2o (CH
2)
3si (OCH
3)
3, purchased from Debang Chemical New Material Co., Ltd., trade mark DB-560, the second silane coupling agent is CH
2=C (CH
3) COO (CH
2)
3si (OCH
3)
3, purchased from Debang Chemical New Material Co., Ltd., trade mark DB-570, the weight ratio of the first silane coupling agent and the second silane coupling agent is 4:1.
The water-soluble silicate (metasilicate pentahydrate sodium, purchased from Qingdao great Run Chemical Co., Ltd.) of whole uniform liquid A and 1 weight part is mixed to evenly under the stirring velocity of 1500 revs/min, obtains uniform liquid B.
By the cilicon oxide filler (nano silicon dioxide sol of whole uniform liquid B 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) be mixed under the stirring velocity of 1500 revs/min evenly, obtain uniform liquid C.
By the water-soluble film-forming resin of whole uniform liquid C and 2.4 weight parts (in solid), ((Silomer8861 emulsion is (purchased from RichdaleSpecialChemicalsInc. for water-soluble silicon third film-forming resin, Rui De special chemical company, solid content is 43 % by weight))) be mixed under the stirring velocity of 1500 revs/min evenly, obtain uniform liquid D.Uniform liquid D is the surface conversion layer forming agent of the present embodiment.
Comparative example 1
Conversion surface layers forming agent is prepared according to the method for embodiment 1, unlike, first add water, silane coupling agent, water-soluble silicate, cilicon oxide filler and water-soluble film-forming resin in the container that mixing is used simultaneously, be mixed under the stirring velocity of 1500 revs/min more evenly, obtain the surface conversion layer forming agent of this comparative example.
Comparative example 2
Conversion surface layers forming agent is prepared according to the method for embodiment 1, unlike, water, water-soluble film-forming resin, water-soluble silicate, cilicon oxide filler and silane coupling agent are mixed successively, obtains the surface conversion layer forming agent 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
Conversion surface layers forming agent is prepared according to the method for embodiment 1, unlike, water, silane coupling agent, cilicon oxide filler, water-soluble silicate and water-soluble film-forming resin are mixed successively, obtains the surface conversion layer forming agent of this comparative example.That is, the application of sample order of water-soluble silicate and cilicon oxide filler is exchanged.
Comparative example 4
Conversion surface layers forming agent is prepared according to the method for embodiment 1, unlike, the silane coupling agent of 1.6 weight parts is all the first silane coupling agent, not containing the second silane coupling agent.
Comparative example 5
Conversion surface layers forming agent is prepared according to the method for embodiment 1, unlike, the silane coupling agent of 1.6 weight parts is all the second silane coupling agent, not containing the first silane coupling agent.
Embodiment 2
Be mixed under the stirring velocity of 1500 revs/min evenly by the silane coupling agent (being made up of the first silane coupling agent and the second silane coupling agent) of the water of 25 weight parts and 1.4 weight parts, obtain uniform liquid A, wherein, the first silane coupling agent is CH
2(O) CHCH
2o (CH
2)
3si (OC
2h
5)
3, purchased from Debang Chemical New Material Co., Ltd., trade mark DB-563, the second silane coupling agent is CH
2=C (CH
3) COO (CH
2)
3si (OCH
3)
3, purchased from Debang Chemical New Material Co., Ltd., trade mark DB-570, the weight ratio of the first silane coupling agent and the second silane coupling agent is 3.7:1.
The water-soluble silicate (potassium silicate, purchased from Baoding Run Feng Industrial Co., Ltd.) of whole uniform liquid A and 1 weight part is mixed to evenly under the stirring velocity of 1500 revs/min, obtains uniform liquid B.
The cilicon oxide filler (nano silicon dioxide sol, purchased from Asahi Denka Co., Ltd., the trade mark is AT-30, and weight is in silicon-dioxide) 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 water-soluble film-forming resin of whole uniform liquid C and 2.1 weight parts (in solid), ((Silomer8861 emulsion is (purchased from RichdaleSpecialChemicalsInc. for water-soluble silicon third film-forming resin, Rui De special chemical company, solid content is 43 % by weight))) be mixed under the stirring velocity of 1500 revs/min evenly, obtain uniform liquid D.Uniform liquid D is the surface conversion layer forming agent of the present embodiment.
Embodiment 3
Be mixed under the stirring velocity of 1500 revs/min evenly by the silane coupling agent (being made up of the first silane coupling agent and the second silane coupling agent) of the water of 40 weight parts and 1.8 weight parts, obtain uniform liquid A, wherein, the first silane coupling agent is CH
2(O) CHCH
2o (CH
2)
3siCH
3(OCH
3)
2, purchased from Debang Chemical New Material Co., Ltd., trade mark DB-561, the second silane coupling agent is CH
2=C (CH
3) COO (CH
2)
3si (OCH
3)
3, purchased from Debang Chemical New Material Co., Ltd., trade mark DB-570, the weight ratio of the first silane coupling agent and the second silane coupling agent is 4.3:1.
The water-soluble silicate (metasilicate pentahydrate sodium, purchased from Qingdao great Run Chemical Co., Ltd.) of whole uniform liquid A and 1 weight part is mixed to evenly under the stirring velocity of 1500 revs/min, obtains uniform liquid B.
The cilicon oxide filler (nano silicon dioxide sol, purchased from Asahi Denka Co., Ltd., the trade mark is AT-30, and weight is in silicon-dioxide) of whole uniform liquid B and 0.85 weight part is mixed to evenly under the stirring velocity of 1500 revs/min, obtains uniform liquid C.
By the water-soluble film-forming resin of whole uniform liquid C and 2.7 weight parts (in solid), ((Silomer8861 emulsion is (purchased from RichdaleSpecialChemicalsInc. for water-soluble silicon third film-forming resin, Rui De special chemical company, solid content is 43 % by weight))) be mixed under the stirring velocity of 1500 revs/min evenly, obtain uniform liquid D.Uniform liquid D is the surface conversion layer forming agent of the present embodiment.
Embodiment 4
Be mixed under the stirring velocity of 1500 revs/min evenly by the silane coupling agent (being made up of the first silane coupling agent and the second silane coupling agent) of the water of 90 weight parts and 0.6 weight part, obtain uniform liquid A, wherein, the first silane coupling agent is CH
2(O) CHCH
2o (CH
2)
3si (OCH
3)
3, purchased from Debang Chemical New Material Co., Ltd., trade mark DB-560, the second silane coupling agent is CH
2=C (CH
3) COO (CH
2)
3si (OCH
3)
3, purchased from Debang Chemical New Material Co., Ltd., trade mark DB-570, the weight ratio of the first silane coupling agent and the second silane coupling agent is 4.3:1.
The water-soluble silicate (metasilicate pentahydrate sodium, purchased from Qingdao great Run Chemical Co., Ltd.) of whole uniform liquid A and 1 weight part is mixed to evenly under the stirring velocity of 1500 revs/min, obtains uniform liquid B.
By the cilicon oxide filler (nano silicon dioxide sol of whole uniform liquid B 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) be mixed under the stirring velocity of 1500 revs/min evenly, obtain uniform liquid C.
By the water-soluble film-forming resin of whole uniform liquid C and 6.5 weight parts (in solid), ((Silomer8861 emulsion is (purchased from RichdaleSpecialChemicalsInc. for water-soluble silicon third film-forming resin, Rui De special chemical company, solid content is 43 % by weight))) be mixed under the stirring velocity of 1500 revs/min evenly, obtain uniform liquid D.Uniform liquid D is the surface conversion layer forming agent of the present embodiment.
Embodiment 5
Be mixed under the stirring velocity of 1500 revs/min evenly by the silane coupling agent (being made up of the first silane coupling agent and the second silane coupling agent) of the water of 15 weight parts and 4.5 weight parts, obtain uniform liquid A, wherein, the first silane coupling agent is CH
2(O) CHCH
2o (CH
2)
3si (OCH
3)
3, purchased from Debang Chemical New Material Co., Ltd., trade mark DB-560, the second silane coupling agent is CH
2=C (CH
3) COO (CH
2)
3si (OCH
3)
3, purchased from Debang Chemical New Material Co., Ltd., trade mark DB-570, the weight ratio of the first silane coupling agent and the second silane coupling agent is 3.7:1.
The water-soluble silicate (metasilicate pentahydrate sodium, purchased from Qingdao great Run Chemical Co., Ltd.) of whole uniform liquid A and 1 weight part is mixed to evenly under the stirring velocity of 1500 revs/min, obtains uniform liquid B.
By the cilicon oxide filler (nano silicon dioxide sol of whole uniform liquid B 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) be mixed under the stirring velocity of 1500 revs/min evenly, obtain uniform liquid C.
By the water-soluble film-forming resin of whole uniform liquid C and 1.0 weight parts (in solid), ((Silomer8861 emulsion is (purchased from RichdaleSpecialChemicalsInc. for water-soluble silicon third film-forming resin, Rui De special chemical company, solid content is 43 % by weight))) be mixed under the stirring velocity of 1500 revs/min evenly, obtain uniform liquid D.Uniform liquid D is the surface conversion layer forming agent of the present embodiment.
Embodiment 6
Conversion surface layers forming agent is prepared according to the method for embodiment 1, unlike, the first silane coupling agent is CH
2(O) CHCH
2o (CH
2)
3siCH
3(OC
2h
5)
2(purchased from Debang Chemical New Material Co., Ltd., trade mark DB-562).
Embodiment 7
Conversion surface layers forming agent is prepared according to the method for embodiment 1, unlike, the first silane coupling agent is
(CH
2)
2si (OCH
3)
3(purchased from Debang Chemical New Material Co., Ltd., trade mark DB-186).
Embodiment 8
Conversion surface layers forming agent is prepared according to the method for embodiment 1, unlike, the first silane coupling agent is
(CH
2)
2si (OC
2h
5)
3(purchased from Debang Chemical New Material Co., Ltd., trade mark DB-1770).
Embodiment 9
Conversion surface layers forming agent is prepared according to the method for embodiment 1, unlike, the second silane coupling agent is CH
2=C (CH
3) COO (CH
2)
3si (OC
2h
5)
3(purchased from Debang Chemical New Material Co., Ltd., trade mark DB-572).
Embodiment 10
Conversion surface layers forming agent is prepared according to the method for embodiment 1, unlike, the second silane coupling agent is CH
2=C (CH
3) COO (CH
2)
3siCH
3(OCH
3)
2(purchased from Debang Chemical New Material Co., Ltd., trade mark DB-571).
Embodiment 11
Conversion surface layers forming agent is prepared according to the method for embodiment 1, unlike, the second silane coupling agent is CH
2=C (CH
3) COO (CH
2)
3siCH
3(OC
2h
5)
2(purchased from Rule, Shanghai Chemical trade company limited, trade mark Luer-1512).
Embodiment 12
Conversion surface layers forming agent is prepared according to the method for embodiment 1, unlike, the weight ratio of the first silane coupling agent and the second silane coupling agent is 3:1.
Embodiment 13
Conversion surface layers forming agent is prepared according to the method for embodiment 1, unlike, the weight ratio of the first silane coupling agent and the second silane coupling agent is 5:1
Embodiment 14
Conversion surface layers forming agent 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 in the material after water and silane coupling agent being mixed, 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) and mix, wherein, relative to the water-soluble silicate of 1 weight part, the consumption of lubricating auxiliary agent is 0.6 weight part.
Embodiment 15
Conversion surface layers forming agent is prepared according to the method for embodiment 14, unlike, do not add lubricating auxiliary agent.
Embodiment 16
Conversion surface layers forming agent is prepared according to the method for embodiment 1, unlike, 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 in the material after water and silane coupling agent being mixed, 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 DEG C, 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 DEG C, acid number is 14-21mgKOH/g) and mix, wherein, relative to the water-soluble silicate of 1 weight part, the consumption of lubricating auxiliary agent is 0.5 weight part.
Embodiment 17
Conversion surface layers forming agent 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 in the material after water and silane coupling agent being mixed, 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) and mix, wherein, relative to the water-soluble silicate of 1 weight part, the consumption of lubricating auxiliary agent is 0.7 weight part.
Embodiment 18
Conversion surface layers forming agent 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 in the material after water and silane coupling agent being mixed, 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) and mix, 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 surface conversion layer forming agent that Example 1-18 and comparative example 1-4 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 after processing 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 uses XRF(fluorescence spectrophotometer) survey meter measure numerical value.Wherein, this prepares the surface conversion layer forming agent used in embodiment is all stored the surface conversion layer forming agent of 1 day after having prepared (namely obtaining uniform liquid D).
Preparation embodiment 2-4
According to the steel plate galvanized after the method preparation process preparing embodiment 1, be all after having prepared (namely obtaining uniform liquid D), stored the surface conversion layer forming agent of 60,120 and 180 days unlike, the surface conversion layer forming agent of use.
Testing example 1
By the requirement specified in GB/T101251997, carry out neutral salt spray test, measure the corrosion resisting property of the steel plate galvanized after the process of preparation embodiment 1-4 respectively.It is qualified to be considered as by " salt-fog test 144h, corrosion area < 3% ".
On M-2000 ring block type friction and wear tester, the kinetic friction coefficient of the coating of the steel plate galvanized after the process obtained according to its specification sheets mensuration preparation embodiment 1.
Test result as above is as shown in table 1.The storage time of the number of days presentation surface conversion coating forming agent in bracket.
Table 1
Visible according to the data of table 1, the solidity to corrosion of the protective film that surface conversion layer forming agent provided by the invention is formed is very excellent, and the storage endurance of surface conversion layer forming agent provided by the invention is also 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 silane coupling agent is 1.4-1.8 weight part, the weight ratio of the first silane coupling agent and described second silane coupling agent is 3.7-4.3:1, 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 surface conversion layer forming agent is formed 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 surface conversion layer forming agent is formed can be improved further.In addition, according to the data of table 1, preferably, described first silane coupling agent is CH
2(O) CHCH
2o (CH
2)
3si (OCH
3)
3, described second silane coupling agent is CH
2=C (CH
3) COO (CH
2)
3si (OCH
3)
3when, the solidity to corrosion of the protective film that described surface conversion layer forming agent is formed 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 (10)
1. a preparation method for surface conversion layer forming agent, the method comprises and water, silane coupling agent, water-soluble silicate, cilicon oxide filler and water-soluble film-forming resin being mixed successively; Described silane coupling agent contains the first silane coupling agent and the second silane coupling agent; Wherein said first silane coupling agent is CH
2(O) CHCH
2o (CH
2)
3si (OCH
3)
3; Described second silane coupling agent is CH
2=C (CH
3) COO (CH
2)
3si (OCH
3)
3, the weight ratio of described first silane coupling agent and described second silane coupling agent is 3.7-4.3:1.
2. preparation method according to claim 1, wherein, relative to the described water-soluble silicate of 1 weight part, the consumption of described silane coupling agent is 0.5-4.5 weight part, 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. preparation method according to claim 2, wherein, relative to the described water-soluble silicate of 1 weight part, the consumption of described silane 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, and the consumption of water is 25-40 weight part.
4. according to the preparation method in claim 1-3 described in any one, 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.
5. preparation method according to claim 4, wherein, described water-soluble silicon third film-forming resin is Silomer8861 emulsion.
6. according to the preparation method in claim 1-3 described in any one, wherein, this preparation method also comprises: the material after water and silane coupling agent being mixed mixes with lubricating auxiliary agent, 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, relative 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 surface conversion layer forming agent that the preparation method in claim 1-6 described in any one prepares.
8. surface conversion layer forming agent according to claim 7 is preparing the purposes in 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 surface conversion layer forming agent according to claim 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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|---|---|---|---|
| CN201310159989.6A CN104059409B (en) | 2013-05-03 | 2013-05-03 | A kind of surface conversion layer forming agent and its production and use and hot-dip metal plated material |
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|---|---|---|---|
| CN201310159989.6A CN104059409B (en) | 2013-05-03 | 2013-05-03 | A kind of surface conversion layer forming agent and its production and use and hot-dip metal plated material |
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| JP5322000B2 (en) * | 2007-12-07 | 2013-10-23 | ディップソール株式会社 | Surface treatment aqueous solution and treatment method for forming a corrosion-resistant film on zinc or zinc alloy plating |
| CN101891998B (en) * | 2009-05-18 | 2012-11-21 | 攀钢集团钢铁钒钛股份有限公司 | Paint composition and galvanized passivated material |
| CN103031043B (en) * | 2011-09-28 | 2015-06-24 | 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 |
| CN103031042B (en) * | 2011-09-28 | 2015-06-24 | 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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