CN104059479B - Weather resistant application compositions and its production and use and hot-dip metal plated material - Google Patents
Weather resistant application compositions and its production and use and hot-dip metal plated material Download PDFInfo
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Abstract
The invention provides the preparation method of a kind of weather resistant application compositions, the method includes water, silane coupler, water-soluble silicate, cilicon oxide filler and water-soluble film-forming resin successively mix homogeneously.Present invention also offers the weather resistant application compositions prepared according to preparation method as above and above-mentioned weather resistant application compositions purposes in preparing metal material.Present invention also offers a kind of hot-dip metal plated material, this hot-dip metal plated material includes hot-dip metal plated base material and the coating being attached on this hot-dip metal plated base material, and described coating is the cured product of weather resistant application compositions as above.The corrosion resistance of the protecting film that the weather resistant application compositions that the present invention provides is formed is the most excellent.Additionally, the storage endurance of the weather resistant application compositions of present invention offer is the most excellent, can at room temperature store 180 days after preparation completes and not occur obvious character to change and hydraulic performance decline.
Description
Technical field
The present invention relates to metal protection field, in particular it relates to the preparation method of a kind of weather resistant application compositions, this preparation method the weather resistant application compositions obtained, the purposes of this weather resistant application compositions and hot-dip metal plated material.
Background technology
Hot-dip metal plated material, including hot-dip galvanized metal material and hot-dip aluminizing zinc metal material, in order to prevent corrosion, all can be in the surface of hot-dip metal plated material one layer of weather resistant application compositions of coating to form protecting film.Thus the performance of weather resistant application compositions is particularly significant for the anti-corrosion of hot-dip metal plated material.
Such as, CN101608306A discloses a kind of passivating solution, fall within a kind of weather resistant application compositions, it is characterized in that, this passivating solution is the aqueous solution containing water-soluble molybdenum compound, boric acid, water soluble organic substance and Ludox, wherein, described water soluble organic substance is the mixture of alcohol and organic carboxyl acid.
But it is demonstrated experimentally that the corrosion resistance of the protecting film of this weather resistant application compositions formation is the most poor.
Summary of the invention
The defect that the corrosion resistance of the protecting film that it is an object of the invention to overcome existing weather resistant application compositions to be formed is poor, it is provided that a kind of weather resistant application compositions that can form the preferable protecting film of corrosion resistance.
To achieve these goals, the invention provides the preparation method of a kind of weather resistant application compositions, the method includes water, silane coupler, water-soluble silicate, cilicon oxide filler and water-soluble film-forming resin successively mix homogeneously；Described silane coupler includes that the first silane coupler and the second silane coupler, described first silane coupler are R-Si (OCH3)3、R-Si(OC2H5)3、R-SiCH3(OCH3)2And R-SiCH3(OC2H5)2In at least one, and R is each independently selected from NH2(CH2)2NH(CH2)3-、NH2(CH2)2NHCH2CH(CH3)CH2-、HO(CH2)2NH(CH2)2NH(CH2)3-or NH2(CH2)2NH(CH2)2NH(CH2)3-；Described second silane coupler is R1-Si(OCH3)3、R1-Si(OC2H5)3、R1-SiCH3(OCH3)2And R1-SiCH3(OC2H5)2In at least one, and R1It is each independently selected from CH2(O)CHCH2O(CH2)3-or
Present invention also offers the weather resistant application compositions prepared according to preparation method as above.
Present invention also offers above-mentioned weather resistant application compositions purposes in preparing metal material.
Present invention also offers a kind of hot-dip metal plated material, this hot-dip metal plated material includes hot-dip metal plated base material and the coating being attached on this hot-dip metal plated base material, described hot-dip metal plated base material is at least one in galvanizing 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 weather resistant application compositions as above.
By technique scheme, the corrosion resistance of the protecting film that the weather resistant application compositions that the present invention provides is formed is the most excellent.Additionally, the storage endurance of the weather resistant application compositions of present invention offer is the most excellent, can at room temperature store 180 days after preparation completes and not occur obvious character to change and hydraulic performance decline.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that detailed description of the invention described herein is merely to illustrate and explains the present invention, it is not limited to the present invention.
The invention provides the preparation method of a kind of weather resistant application compositions, the method includes water, silane coupler, water-soluble silicate, cilicon oxide filler and water-soluble film-forming resin successively mix homogeneously；Described silane coupler includes that the first silane coupler and the second silane coupler, described first silane coupler are R-Si (OCH3)3、R-Si(OC2H5)3、R-SiCH3(OCH3)2And R-SiCH3(OC2H5)2In at least one, and R is each independently selected from NH2(CH2)2NH(CH2)3-、NH2(CH2)2NHCH2CH(CH3)CH2-、HO(CH2)2NH(CH2)2NH(CH2)3-or NH2(CH2)2NH(CH2)2NH(CH2)3-；Described second silane coupler is R1-Si(OCH3)3、R1-Si(OC2H5)3、R1-SiCH3(OCH3)2And R1-SiCH3(OC2H5)2In at least one, and R1It is each independently selected from CH2(O)CHCH2O(CH2)3-or
Wherein, in detail, the method includes: (1), by water and described silane coupler mix homogeneously, obtains uniform liquid A；(2) by described uniform liquid A and water-soluble silicate mix homogeneously, uniform liquid B is obtained；(3) by described uniform liquid B and cilicon oxide filler mix homogeneously, uniform liquid C is obtained；(4) described uniform liquid C is mixed homogeneously with water-soluble film-forming resin, obtain uniform liquid D.Wherein, there is no particular limitation for the method for mix homogeneously, as long as uniform stablizing mutually can be obtained, preferably makes mixing more uniform by stirring.
Preparation method according to the weather resistant application compositions that the present invention provides, wherein, described water-soluble silicate relative to 1 weight portion, the consumption of described silane coupler can be 0.5-4.5 weight portion, and the weight ratio of described first silane coupler and described second silane coupler can be 1:0.1-1；Preferably, the consumption of described silane coupler is 1.4-1.8 weight portion, and the weight ratio of described first silane coupler and described second silane coupler is 1:0.4-0.6.
Wherein, relative to the described water-soluble silicate of 1 weight portion, the consumption of described cilicon oxide filler can be 0.25-2.2 weight portion, preferably 0.6-0.85 weight portion.
Wherein, relative to the described water-soluble silicate of 1 weight portion, in terms of solid, the consumption of described water-soluble film-forming resin can be 0.8-6.8 weight portion, preferably 2.1-2.7 weight portion.Solid is with for calculating or representing that the solid implication of solid content is identical herein, is water-soluble film-forming resin and removes remaining composition after solvent.
Wherein, relative to the described water-soluble silicate of 1 weight portion, the consumption of water is 10-100 weight portion, preferably 25-40 weight portion.It should be noted that the consumption of water described in the present invention refers to the amount of the water additionally added, do not include in above-mentioned other component added with solution or emulsion mode with the amount of water.
According to the preparation method of the weather resistant application compositions that the present invention provides, wherein, under preferable case, described first silane coupler is NH2(CH2)2NH(CH2)3Si(OCH3)3、NH2(CH2)2NH(CH2)3Si(OC2H5)3、NH2(CH2)2NH(CH2)3SiCH3(OCH3)2、NH2(CH2)2NHCH2CH(CH3)CH2CH3(OCH3)2、HO(CH2)2NH(CH2)2NH(CH2)3SiCH3(OCH3)2、NH2(CH2)2NH(CH2)2NH(CH2)3SiCH3(OCH3)2And NH2(CH2)2NH(CH2)2NH(CH2)3Si(OCH3)3In at least one.Wherein, NH2(CH2)2NH(CH2)3Si(OCH3)3(referred to as N-aminoethyl-γ-aminopropyltrimethoxysilane), NH2(CH2)2NH(CH2)3Si(OC2H5)3(referred to as N-aminoethyl-gamma-aminopropyl-triethoxy-silane), NH2(CH2)2NH(CH2)3SiCH3(OCH3)2(referred to as N-aminoethyl-γ-aminopropyltriethoxy dimethoxysilane), NH2(CH2)2NHCH2CH(CH3)CH2CH3(OCH3)2(referred to as aminoethyl ammonia isobutyl methyl dimethoxysilane), HO (CH2)2NH(CH2)2NH(CH2)3SiCH3(OCH3)2(referred to as 3-(2-ethoxy aminoethyl)-aminopropyltriethoxy dimethoxysilane), NH2(CH2)2NH(CH2)2NH(CH2)3SiCH3(OCH3)2(referred to as diethylenetriamine base hydroxypropyl methyl dimethoxysilane) and NH2(CH2)2NH(CH2)2NH(CH2)3Si(OCH3)3(referred to as diethylenetriamine base propyl trimethoxy silicane) can serve as the first silane coupler, the commercially available commodity shown in various above-mentioned chemical formula that can be used as silane coupler may be used to the present invention, such as purchased from the commercially available product that the trade mark is DB-792, DB-793, DB-602, DB-604, DB-2602, DB-5551 and DB-4552 of Debang Chemical New Material Co., Ltd..Wherein, the most described first silane coupler is NH2(CH2)2NH(CH2)3Si(OCH3)3、NH2(CH2)2NH(CH2)3Si(OC2H5)3And NH2(CH2)2NH(CH2)3SiCH3(OCH3)2In at least one.
According to the preparation method of the weather resistant application compositions that the present invention provides, wherein, under preferable case, described second silane coupler is CH2(O)CHCH2O(CH2)3Si(OCH3)3、CH2(O)CHCH2O(CH2)3Si(OC2H5)3、CH2(O)CHCH2O(CH2)3SiCH3(OCH3)2、CH2(O)CHCH2O(CH2)3SiCH3(OC2H5)2、(CH2)2Si(OCH3)3With(CH2)2Si(OC2H5)3In at least one.Wherein, CH2(O)CHCH2O(CH2)3Si(OCH3)3(referred to as γ-glycydoxy trimethoxy silane), CH2(O)CHCH2O(CH2)3Si(OC2H5)3(referred to as γ-glycydoxy triethoxysilane), CH2(O)CHCH2O(CH2)3SiCH3(OCH3)2(referred to as γ-glycydoxy methyl dimethoxysilane), CH2(O)CHCH2O(CH2)3SiCH3(OC2H5)2(referred to as γ-glycydoxy methyldiethoxysilane),(referred to as 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane) and(referred to as 2-(3,4-epoxycyclohexyl) ethyl triethoxysilane) can serve as the second silane coupler, the commercially available commodity shown in various above-mentioned chemical formula that can be used as silane coupler may be used to the present invention, such as purchased from the commercially available product that the trade mark is DB-560, DB-563, DB-561, DB-562, DB-186 and DB-1770 of Debang Chemical New Material Co., Ltd..Wherein, the most described second silane coupler is CH2(O)CHCH2O(CH2)3Si(OCH3)3。
According to the preparation method of the weather resistant application compositions that the present invention provides, wherein, described water-soluble silicate can be sodium silicate and/or potassium silicate.Described sodium silicate can be at least one in anhydrous sodium metasilicate, SODIUM METASILICATE PENTAHYDRATE and nine water sodium silicate.Further, the consumption of described water-soluble silicate is to calculate with the amount of anhydrous silicate.
Preparation method according to the weather resistant application compositions that the present invention provides, wherein, described cilicon oxide filler does not has 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, more preferably 5-30nm, such as, the commercially available product that the trade mark is AT-30, AT-30S, AT-40, AT-30A and AT-20 purchased from Asahi Denka Co., Ltd., or the commercially available product that the trade mark is SS-25 and SS-30 purchased from Shandong Bai Te new material company limited can be used.And, the consumption of cilicon oxide filler is to calculate with the weight of silicon oxide itself, the consumption of such as nano silicon dioxide sol is to calculate with the amount of the silicon dioxide in colloidal sol, the numerical computations obtained after being i.e. multiplied by its dioxide-containing silica percent (weight) with the weight of nano silicon dioxide sol.
nullPreparation method according to the weather resistant application compositions that the present invention provides，Wherein，Described water-soluble film-forming resin can be various water miscible and can be used in the modified 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 present invention not particularly requirement，As long as can be used in film forming，Such as，Described water-soluble film-forming resin can be for water-soluble polyester film-forming resin (i.e. water-soluble film-forming resin obtained by polyalcohols monomer and polynary acrylic monomer are polymerized，Such as purchased from Guangzhou Lapo Fine Chemicals Co., Ltd.，The polyester resin of trade mark CB2200)、Water solublity phenylpropyl alcohol film-forming resin (i.e. water-soluble film-forming resin obtained by styrene monomer and acrylic acid (ester) class monomer are polymerized，Such as purchased from Guangzhou Chao Long Chemical Industry Science Co., Ltd，The trade mark is the styrene-acrylic emulsion of xy-108b)、Soluble epoxide film-forming resin (i.e. water-soluble film-forming resin obtained by the monomer containing epoxy radicals is polymerized，Such as purchased from Dongguan City Heima Chemical Co., Ltd.，The trade mark is the epoxy resin of BH620)、Soluble polyurethane film-forming resin (i.e. water-soluble film-forming resin obtained by multicomponent isocyanate class monomer and multi-hydroxy compounds monomer are polymerized，Such as purchased from Jinjiang, Fujian Province Jian Hua company，The polyurethane resin of the trade mark 812)、Water-soluble silicon the third film-forming resin (i.e. water-soluble film-forming resin obtained by silicone monomer and acrylic acid (ester) class monomer are polymerized，Make the country prosperous paint company TC-05 type silicone acrylic emulsion in such as Qingdao，Solid content is 48 weight %)、Water-soluble acrylic film-forming resin is (i.e. by water-soluble film-forming resin obtained by the polymerization of acrylic acid (ester) class monomer，Such as purchased from the acrylic resin that the trade mark is A-3418 of Guangzhou Ou Peng chemical industry) and water-soluble fluorine carbon film-forming resin (i.e. water-soluble film-forming resin obtained by fluorinated monomer is polymerized，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 solublity phenylpropyl alcohol film-forming resin, soluble epoxide film-forming resin, water-soluble silicon the third film-forming resin, water-soluble acrylic film-forming resin, soluble polyurethane film-forming resin and water-soluble polyester film-forming resin.It is highly preferred that wherein, described water-soluble silicon the third film-forming resin is Silomer8861 emulsion (purchased from RichdaleSpecialChemicalsInc., Rui De special chemical company).
Preparation method according to the weather resistant application compositions that the present invention provides, wherein, in order to improve the greasy property of the protecting film of formation further, under preferable case, this preparation method also includes: mixed homogeneously with lubricating auxiliary agent by the material after water and silane coupler mix homogeneously, and described lubricating auxiliary agent is one or more in the water-based emulsion of the water-based emulsion of dimethicone, polyether-modified polysiloxanes, the water-based emulsion of Tissuemat E and OPE.
It is highly preferred that relative to the described water-soluble silicate of 1 weight portion, the content of described lubricating auxiliary agent is 0.2-1.8 weight portion, more preferably 0.5-0.7 weight portion.
Wherein, the solid content of the water-based emulsion of described dimethicone can be 10-90 weight %, preferably 30-80 weight %.It should be noted that the water-based emulsion of dimethicone is when for preparing the weather resistant application compositions of present invention offer, its consumption refers to the numerical value that the gross weight of water-based emulsion obtains after being multiplied by its solid content.It should be noted that the solid content of the water-based emulsion of described dimethicone refers to prepare the content of the dimethicone used by the water-based emulsion of described dimethicone.Described dimethicone refers to water-insoluble unmodified dimethicone.
Wherein, the dimethyl-silicon oil viscosity in the water-based emulsion of described dimethicone can be 500-50000mPa S, preferably 1000-40000mPa S, more preferably 1500-30000mPa S.
Wherein, described polyether-modified polysiloxanes is commonly called as water-soluble dimethyl silicone oil, and existing various water-soluble dimethyl silicone oil all can be used for realizing the purpose of the present invention as described lubricating auxiliary agent in the present invention.The most described polyether-modified polysiloxanes be viscosity be 100-10000mPa S, the water-soluble dimethyl silicone oil of preferably 500-8000mPa S, more preferably 1000-6000mPa S, the most preferably 2000-5000mPa S.
It should be noted that in the case of 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 Tissuemat E can be the water-based emulsion that conventionally will obtain after Tissuemat E emulsifying, and the solid content of the water-based emulsion of described Tissuemat E can be 30-60 weight %, preferably 40-50 weight %.It should be noted that the water-based emulsion of Tissuemat E is when for preparing the weather resistant application compositions of present invention offer, its consumption refers to the numerical value that the gross weight of water-based emulsion obtains after being multiplied by its solid content.
Wherein, the fusing point of the Tissuemat E in the water-based emulsion of described Tissuemat E can be 90-130 DEG C, preferably 100-120 DEG C, more preferably 105-115 DEG C.
Wherein, the water-based emulsion of described OPE can be the water-based emulsion that conventionally will obtain after OPE emulsifying, and the solid content of the water-based emulsion of described OPE can be 30-60 weight %, preferably 40-50 weight %.It should be noted that the water-based emulsion of OPE is when for preparing the weather resistant application compositions of present invention offer, its consumption refers to the numerical value that the gross weight of water-based emulsion obtains after being multiplied by its solid content.
Wherein, the fusing point of the OPE in the water-based emulsion of described OPE can be 80-120 DEG C, preferably 90-115 DEG C, more preferably 100-110 DEG C.
It should be noted that in the case of illustrating on the contrary in the present invention, the fusing point of Tissuemat E and OPE refers to the numerical value that the mensuration according to GB/T2539-2008 pertroleum wax fusing point-cooling curve method measures.
Wherein, the acid number of the OPE in the water-based emulsion of described OPE can be 5-60mgKOH/g, 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 weather resistant application compositions prepared according to preparation method as above.Wherein, preparation method as above obtains add water-soluble film-forming resin mix homogeneously after material (that is, the uniform liquid D obtained) may act as the present invention weather resistant application compositions use.
Additionally, the weather resistant application compositions of the present invention can also contain other various components not affecting weather resistant application compositions character, such as one or more in dyestuff, pigment, dispersant and defoamer.On the basis of the gross weight of this weather resistant application compositions, the content of other component is less than 20 weight %, preferably more than 10 weight %.Described defoamer can be various defoamer well known in the art, such as one or more in polyethers defoamer, high-carbon alcohol defoaming agent and silicon class defoamer etc..More specifically, one or more during described defoamer can be the SD-401 series defoamer commercially available from such as Co., Ltd of Dongying dan big Creative Science and Technology Co. Ltd.Under preferable case, on the basis of the total amount of described weather resistant application compositions, the content of described defoamer is 0.01-0.05 weight %.
Correspondingly, the preparation method of the weather resistant application compositions that the present invention provides can also include adding other various components not affecting weather resistant application compositions character step of mix homogeneously.These other various components not affecting weather resistant application compositions character can add after adding water-soluble film-forming resin.
The weather resistant application compositions of the present invention can directly use without dilution.
Present invention also offers above-mentioned weather resistant application compositions purposes in preparing metal material.Above-mentioned weather resistant application compositions can be used for preparing various metal material in the way of this area is conventional.
The hot-dip metal plated material provided according to the present invention, this hot-dip metal plated material includes galvanizing metal base and the coating being attached on this hot-dip metal plated base material, described hot-dip metal plated base material is at least one in galvanizing metal base, hot-dip aluminizing zinc metal base and hot-dip aluminizing zinc magnesium metal base material, and described coating is the cured product of weather resistant application compositions as above.
Wherein, described galvanizing metal base can be the metal base containing zinc coating, and in described zinc coating, the content of zinc can be 92.5-95.5 weight %.Described zinc coating also can contain other conventional ingredient, such as silicon.
Wherein, described hot-dip aluminizing zinc metal base can be the metal base containing zinc-aluminium coating, and in described zinc-aluminium coating, the content of zinc can be 41.5-43.5 weight %, and the content of aluminum can be 51.5-55.0 weight %.Described zinc-aluminium coating also can contain other conventional ingredient, such as silicon.
Wherein, hot-dip aluminizing zinc magnesium metal base material can be the metal base containing aluminum zinc-magnesium coating, and in described aluminum zinc-magnesium coating, the content of zinc can be 85.5-99.2 weight %, and the content of aluminum can be 0.2-11 weight %, and the content of magnesium can be 0.5-3 weight %.Described aluminum zinc-magnesium coating also can contain other conventional ingredient, such as silicon.
The hot-dip metal plated material provided according to the present 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 is to use XRF(fluorescence spectrophotometer) measuring instrument measure numerical value.
The hot-dip metal plated material provided according to the present invention, wherein, the method adhering to described coating on hot-dip metal plated base material can include being attached on the surface of hot-dip metal plated base material described weather resistant application compositions, then it is dried, the temperature being dried can be 60-120 DEG C, being preferably 90-110 DEG C, the time can be the 0.5-3 second.The consumption of described weather resistant application compositions can be determined according to the thickness of coating.
Wherein, described dry method, can be one or more in hot air drying, sensing heating and infrared radiation heating.
In the present invention, in the case of not doing contrary explanation, the volume of all liq and solid refers both to 20 DEG C, the volume of 1 standard atmosphere pressure.
Hereinafter by embodiment, the present invention will be explained in further detail.
Embodiment 1
Mixing the water of 28 weight portions and the silane coupler (being made up of the first silane coupler and the second silane coupler) of 1.6 weight portions to uniformly under the mixing speed of 1500 revs/min, obtain uniform liquid A, wherein, the first silane coupler is NH2(CH2)2NH(CH2)3Si(OCH3)3, purchased from Debang Chemical New Material Co., Ltd., trade mark DB-792, the second silane coupler is CH2(O)CHCH2O(CH2)3Si(OCH3)3, purchased from Debang Chemical New Material Co., Ltd., trade mark DB-560, the weight ratio of the first silane coupler and the second silane coupler is 1:0.5.
The water-soluble silicate (metasilicate pentahydrate sodium, purchased from Qingdao great Run Chemical Co., Ltd.) of whole uniform liquid A and 1 weight portion is mixed to uniformly under the mixing speed of 1500 revs/min, obtains uniform liquid B.
By whole uniform liquid B and the cilicon oxide filler (nano silicon dioxide sol of 0.72 weight portion, purchased from Shandong Bai Te new material company limited, the trade mark is SS-30, and weight is in terms of silicon dioxide) mix under the mixing speed of 1500 revs/min to uniformly, obtain uniform liquid C.
By the water-soluble film-forming resin of whole uniform liquid C and 2.4 weight portions (in terms of solid), ((Silomer8861 emulsion is (purchased from RichdaleSpecialChemicalsInc. for water-soluble silicon the third film-forming resin, Rui De special chemical company, solid content is 43 weight %))) mix under the mixing speed of 1500 revs/min to uniformly, obtain uniform liquid D.Uniform liquid D is the weather resistant application compositions of the present embodiment.
Comparative example 1
Weather resistant application compositions is prepared according to the method for embodiment 1, except for the difference that, water, silane coupler, water-soluble silicate, cilicon oxide filler and water-soluble film-forming resin first it is simultaneously introduced in the container used by mixing, mix under the mixing speed of 1500 revs/min again to uniformly, obtain the weather resistant application compositions of this comparative example.
Comparative example 2
Prepare weather resistant application compositions according to the method for embodiment 1, except for the difference that, by water, water-soluble film-forming resin, water-soluble silicate, cilicon oxide filler and silane coupler successively mix homogeneously, obtain the weather resistant application compositions of this comparative example.That is, the sample-adding order of silane coupler and water-soluble film-forming resin is exchanged.
Comparative example 3
Prepare weather resistant application compositions according to the method for embodiment 1, except for the difference that, by water, silane coupler, cilicon oxide filler, water-soluble silicate and water-soluble film-forming resin successively mix homogeneously, obtain the weather resistant application compositions of this comparative example.That is, the sample-adding order of water-soluble silicate and cilicon oxide filler is exchanged.
Comparative example 4
Prepare weather resistant application compositions, except for the difference that, all first silane couplers of silane coupler of 1.6 weight portions according to the method for embodiment 1, do not contain the second silane coupler.
Comparative example 5
Prepare weather resistant application compositions, except for the difference that, all second silane couplers of silane coupler of 1.6 weight portions according to the method for embodiment 1, do not contain the first silane coupler.
Embodiment 2
Mixing the water of 25 weight portions and the silane coupler (being made up of the first silane coupler and the second silane coupler) of 1.4 weight portions to uniformly under the mixing speed of 1500 revs/min, obtain uniform liquid A, wherein, the first silane coupler is NH2(CH2)2NH(CH2)3Si(OC2H5)3, purchased from Debang Chemical New Material Co., Ltd., trade mark DB-793, the second silane coupler is CH2(O)CHCH2O(CH2)3Si(OC2H5)3, purchased from Debang Chemical New Material Co., Ltd., trade mark DB-563, the weight ratio of the first silane coupler and the second silane coupler is 1:0.4.
The water-soluble silicate (potassium silicate, purchased from Baoding Run Feng Industrial Co., Ltd.) of whole uniform liquid A and 1 weight portion is mixed to uniformly under the mixing speed 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 terms of silicon dioxide) of whole uniform liquid B and 0.6 weight portion is mixed to uniformly under the mixing speed of 1500 revs/min, obtains uniform liquid C.
By the water-soluble film-forming resin of whole uniform liquid C and 2.1 weight portions (in terms of solid), ((Silomer8861 emulsion is (purchased from RichdaleSpecialChemicalsInc. for water-soluble silicon the third film-forming resin, Rui De special chemical company, solid content is 43 weight %))) mix under the mixing speed of 1500 revs/min to uniformly, obtain uniform liquid D.Uniform liquid D is the weather resistant application compositions of the present embodiment.
Embodiment 3
Mixing the water of 40 weight portions and the silane coupler (being made up of the first silane coupler and the second silane coupler) of 1.8 weight portions to uniformly under the mixing speed of 1500 revs/min, obtain uniform liquid A, wherein, the first silane coupler is NH2(CH2)2NH(CH2)3SiCH3(OCH3)2, purchased from Debang Chemical New Material Co., Ltd., trade mark DB-602, the second silane coupler is CH2(O)CHCH2O(CH2)3SiCH3(OCH3)2, purchased from Debang Chemical New Material Co., Ltd., trade mark DB-561, the weight ratio of the first silane coupler and the second silane coupler is 1:0.6.
The water-soluble silicate (metasilicate pentahydrate sodium, purchased from Qingdao great Run Chemical Co., Ltd.) of whole uniform liquid A and 1 weight portion is mixed to uniformly under the mixing speed 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 terms of silicon dioxide) of whole uniform liquid B and 0.85 weight portion is mixed to uniformly under the mixing speed of 1500 revs/min, obtains uniform liquid C.
By the water-soluble film-forming resin of whole uniform liquid C and 2.7 weight portions (in terms of solid), ((Silomer8861 emulsion is (purchased from RichdaleSpecialChemicalsInc. for water-soluble silicon the third film-forming resin, Rui De special chemical company, solid content is 43 weight %))) mix under the mixing speed of 1500 revs/min to uniformly, obtain uniform liquid D.Uniform liquid D is the weather resistant application compositions of the present embodiment.
Embodiment 4
Mixing the water of 90 weight portions and the silane coupler (being made up of the first silane coupler and the second silane coupler) of 0.6 weight portion to uniformly under the mixing speed of 1500 revs/min, obtain uniform liquid A, wherein, the first silane coupler is NH2(CH2)2NH(CH2)3Si(OCH3)3, purchased from Debang Chemical New Material Co., Ltd., trade mark DB-792, the second silane coupler is CH2(O)CHCH2O(CH2)3Si(OCH3)3, purchased from Debang Chemical New Material Co., Ltd., trade mark DB-560, the weight ratio of the first silane coupler and the second silane coupler is 1:0.4.
The water-soluble silicate (metasilicate pentahydrate sodium, purchased from Qingdao great Run Chemical Co., Ltd.) of whole uniform liquid A and 1 weight portion is mixed to uniformly under the mixing speed of 1500 revs/min, obtains uniform liquid B.
By whole uniform liquid B and the cilicon oxide filler (nano silicon dioxide sol of 2.1 weight portions, purchased from Shandong Bai Te new material company limited, the trade mark is SS-30, and weight is in terms of silicon dioxide) mix under the mixing speed of 1500 revs/min to uniformly, obtain uniform liquid C.
By the water-soluble film-forming resin of whole uniform liquid C and 6.5 weight portions (in terms of solid), ((Silomer8861 emulsion is (purchased from RichdaleSpecialChemicalsInc. for water-soluble silicon the third film-forming resin, Rui De special chemical company, solid content is 43 weight %))) mix under the mixing speed of 1500 revs/min to uniformly, obtain uniform liquid D.Uniform liquid D is the weather resistant application compositions of the present embodiment.
Embodiment 5
Mixing the water of 15 weight portions and the silane coupler (being made up of the first silane coupler and the second silane coupler) of 4.5 weight portions to uniformly under the mixing speed of 1500 revs/min, obtain uniform liquid A, wherein, the first silane coupler is NH2(CH2)2NH(CH2)3Si(OCH3)3, purchased from Debang Chemical New Material Co., Ltd., trade mark DB-792, the second silane coupler is CH2(O)CHCH2O(CH2)3Si(OCH3)3, purchased from Debang Chemical New Material Co., Ltd., trade mark DB-560, the weight ratio of the first silane coupler and the second silane coupler is 1:0.6.
The water-soluble silicate (metasilicate pentahydrate sodium, purchased from Qingdao great Run Chemical Co., Ltd.) of whole uniform liquid A and 1 weight portion is mixed to uniformly under the mixing speed of 1500 revs/min, obtains uniform liquid B.
By whole uniform liquid B and the cilicon oxide filler (nano silicon dioxide sol of 0.3 weight portion, purchased from Shandong Bai Te new material company limited, the trade mark is SS-30, and weight is in terms of silicon dioxide) mix under the mixing speed of 1500 revs/min to uniformly, obtain uniform liquid C.
By the water-soluble film-forming resin of whole uniform liquid C and 1.0 weight portions (in terms of solid), ((Silomer8861 emulsion is (purchased from RichdaleSpecialChemicalsInc. for water-soluble silicon the third film-forming resin, Rui De special chemical company, solid content is 43 weight %))) mix under the mixing speed of 1500 revs/min to uniformly, obtain uniform liquid D.Uniform liquid D is the weather resistant application compositions of the present embodiment.
Embodiment 6
Preparing weather resistant application compositions according to the method for embodiment 1, except for the difference that, the first silane coupler is NH2(CH2)2NHCH2CH(CH3)CH2CH3(OCH3)2(purchased from Debang Chemical New Material Co., Ltd., trade mark DB-604).
Embodiment 7
Preparing weather resistant application compositions according to the method for embodiment 1, except for the difference that, the first silane coupler is HO (CH2)2NH(CH2)2NH(CH2)3SiCH3(OCH3)2(purchased from Debang Chemical New Material Co., Ltd., trade mark DB-2602).
Embodiment 8
Preparing weather resistant application compositions according to the method for embodiment 1, except for the difference that, the first silane coupler is NH2(CH2)2NH(CH2)2NH(CH2)3SiCH3(OCH3)2(purchased from Debang Chemical New Material Co., Ltd., trade mark DB-5551).
Embodiment 9
Preparing weather resistant application compositions according to the method for embodiment 1, except for the difference that, the second silane coupler is CH2(O)CHCH2O(CH2)3SiCH3(OC2H5)2(purchased from Debang Chemical New Material Co., Ltd., trade mark DB-562).
Embodiment 10
Preparing weather resistant application compositions according to the method for embodiment 1, except for the difference that, the second silane coupler is(purchased from Debang Chemical New Material Co., Ltd., trade mark DB-186).
Embodiment 11
Preparing weather resistant application compositions according to the method for embodiment 1, except for the difference that, the second silane coupler is(purchased from Debang Chemical New Material Co., Ltd., trade mark DB-1770).
Embodiment 12
Preparing weather resistant application compositions according to the method for embodiment 1, except for the difference that, the weight ratio of the first silane coupler and the second silane coupler is 1:0.1.
Embodiment 13
Preparing weather resistant application compositions according to the method for embodiment 1, except for the difference that, the weight ratio of the first silane coupler and the second silane coupler is 1:1.
Embodiment 14
Weather resistant application compositions is prepared according to the method for embodiment 1, except for the difference that, (make the country prosperous paint company TC-05 type silicone acrylic emulsion in Qingdao to use water-soluble silicon the third film-forming resin, solid content is 48 weight %) as water-soluble film-forming resin, and (obtaining the material after water and silane coupler mix homogeneously adds lubricating auxiliary agent after the mixing of 1:1 by weight of the water-based emulsion of dimethicone and polyether-modified polysiloxanes, the water-based emulsion of dimethicone is purchased from Nanjing Hua Tuo Chemical Co., Ltd., the trade mark is HTR-1, solid content is 30 weight %, it is to be obtained by after the dimethicone emulsifying that the apparent viscosity at 25 DEG C is 25000mPa S；Polyether-modified polysiloxanes is purchased from Dongguan grand dyeing and finishing auxiliaries for textile Co., Ltd., Factory, and the apparent viscosity at 25 DEG C is 3000mPa S) and mix homogeneously, wherein, relative to the water-soluble silicate of 1 weight portion, the consumption of lubricating auxiliary agent is 0.6 weight portion.
Embodiment 15
Weather resistant application compositions is prepared, except for the difference that, without lubricating auxiliary agent according to the method for embodiment 14.
Embodiment 16
Weather resistant application compositions is prepared according to the method for embodiment 1, except for the difference that, use water solublity phenylpropyl alcohol film-forming resin (purchased from Guangzhou Chao Long Chemical Industry Science Co., Ltd, the trade mark is the styrene-acrylic emulsion of xy-108b) as water-soluble film-forming resin, and (obtaining the material after water and silane coupler mix homogeneously adds lubricating auxiliary agent after the mixing of 1:1 by weight of the water-based emulsion of Tissuemat E and the water-based emulsion of OPE, the water-based emulsion of Tissuemat E is purchased from Dongguan City Hong Guang plastic material business department, solid content is 48 weight %, the fusing point of Tissuemat E is 110-115 DEG C；The water-based emulsion of OPE is purchased from Beijing Zhong Guan special wax company limited, solid content is 48 weight %, the fusing point of OPE is 105-110 DEG C, acid number is 14-21mgKOH/g) and mix homogeneously, wherein, relative to the water-soluble silicate of 1 weight portion, the consumption of lubricating auxiliary agent is 0.5 weight portion.
Embodiment 17
Weather resistant application compositions is prepared according to the method for embodiment 1, except for the difference that, 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 the material after water and silane coupler mix homogeneously will add the lubricating auxiliary agent (water-based emulsion of dimethicone, purchased from Guangzhou Si Luoke Chemical Co., Ltd., solid content is 80 weight %, it is to be obtained by after the dimethicone emulsifying that the apparent viscosity at 25 DEG C is 1500mPa S) and mix homogeneously, wherein, water-soluble silicate relative to 1 weight portion, the consumption of lubricating auxiliary agent is 0.7 weight portion.
Embodiment 18
Weather resistant application compositions is prepared according to the method for embodiment 1, except for the difference that, 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 the material after water and silane coupler mix homogeneously will add the lubricating auxiliary agent (water-based emulsion of dimethicone, purchased from Guangzhou Si Luoke Chemical Co., Ltd., solid content is 80 weight %, it is to be obtained by after the dimethicone emulsifying that the apparent viscosity at 25 DEG C is 1500mPa S) and mix homogeneously, wherein, water-soluble silicate relative to 1 weight portion, the consumption of lubricating auxiliary agent is 0.7 weight portion.
Preparation embodiment 1
The weather resistant application compositions that Example 1-18 and comparative example 1-5 obtain is respectively applied in galvanized steel plain sheet (purchased from Pangang Group Panzhihua Steel Vanadium Co., Ltd., model DX54D, weight % on zinc 95 in zinc coat) surface, hot air drying 2 seconds at 90-110 DEG C, respectively obtain the galvanized steel plain sheet after process.Wherein, coating amount makes the thickness of the coating on the galvanized steel plain sheet after processing be 0.8 micron.The thickness of coating is to use XRF(fluorescence spectrophotometer) measuring instrument measure numerical value.Wherein, the weather resistant application compositions used during this prepares embodiment be all prepared (i.e. obtaining uniform liquid D) after store the weather resistant application compositions of 1 day.
Preparation embodiment 2-4
Galvanized steel plain sheet after processing according to the method preparation of preparation embodiment 1, except for the difference that, the weather resistant application compositions of use be all prepared (i.e. obtaining uniform liquid D) after store the weather resistant application compositions of 60,120 and 180 days.
Testing example 1
By the requirement of regulation in GB/T101251997, carry out neutral salt spray test, measure the corrosion resisting property of the galvanized steel plain sheet after the process of preparation embodiment 1-4 respectively.It is qualified to be considered as by " salt spray test 144h, corrosion area ＜ 3% ".
On M-2000 ring block type friction and wear tester, measure the coefficient of kinetic friction of the coating of the galvanized steel plain sheet after the process that preparation embodiment 1 obtains according to its description.
Test result as above is as shown in table 1.Natural law in bracket represents the storage time of weather resistant application compositions.
Table 1
Data according to table 1 are visible, and the corrosion resistance of the protecting film that the weather resistant application compositions that the present invention provides is formed is the most excellent, and the storage endurance of the weather resistant application compositions of present invention offer is the most excellent.And, data according to table 1 are visible, at the described water-soluble silicate preferably with respect to 1 weight portion, the consumption of described silane coupler is 1.4-1.8 weight portion, the weight ratio of the first silane coupler and described second silane coupler is 1:0.4-6, the consumption of described cilicon oxide filler is 0.6-0.85 weight portion, in terms of solid, the consumption of described water-soluble film-forming resin is 2.1-2.7 weight portion, in the case of the consumption of water is 25-40 weight portion, it is possible to improve the corrosion resistance of the protecting film that described weather resistant application compositions is formed further.And, data according to table 1 are visible, in the case of preferred described water-soluble silicon the third film-forming resin is Silomer8861 emulsion, or in the case of preferred described raw mixture is possibly together with lubricating auxiliary agent, it is possible to improve the lubricity of the protecting film that described weather resistant application compositions is formed further.Additionally, according to the data of table 1, be NH at the most described first silane coupler2(CH2)2NH(CH2)3Si(OCH3)3、NH2(CH2)2NH(CH2)3Si(OC2H5)3And NH2(CH2)2NH(CH2)3SiCH3(OCH3)2In at least one, the most described second silane coupler is CH2(O)CHCH2O(CH2)3Si(OCH3)3In the case of, it is possible to improve the corrosion resistance of the protecting film that described weather resistant application compositions is formed further.
The preferred embodiment of the present invention described in detail above; but, the present invention is not limited to the detail in above-mentioned embodiment, in the technology concept of the present invention; technical scheme can be carried out multiple simple variant, these simple variant belong to protection scope of the present invention.
It is further to note that, each concrete technical characteristic described in above-mentioned detailed description of the invention, in the case of reconcilable, can be combined by any suitable means, in order to avoid unnecessary repetition, various possible compound modes are illustrated by the present invention the most separately.
Additionally, can also carry out combination in any between the various different embodiment of the present invention, as long as it is without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (13)
1. a preparation method for weather resistant application compositions, the method includes water, silane coupler, water-soluble silicate, cilicon oxide filler and water-soluble film-forming resin successively mix homogeneously；Described silane coupler includes that the first silane coupler and the second silane coupler, described first silane coupler are R-Si (OCH3)3、R-Si(OC2H5)3、R-SiCH3(OCH3)2And R-SiCH3(OC2H5)2In at least one, and R is each independently selected from NH2(CH2)2NH(CH2)3-、NH2(CH2)2NHCH2CH(CH3)CH2-、HO(CH2)2NH(CH2)2NH(CH2)3-or NH2(CH2)2NH(CH2)2NH(CH2)3-；Described second silane coupler is R1-Si(OCH3)3、R1-Si(OC2H5)3、R1-SiCH3(OCH3)2And R1-SiCH3(OC2H5)2In at least one, and R1It is each independently selected from CH2(O)CHCH2O(CH2)3-。
Preparation method the most according to claim 1, wherein, described water-soluble silicate relative to 1 weight portion, the consumption of described silane coupler is 0.5-4.5 weight portion, the weight ratio of described first silane coupler and described second silane coupler is 1:0.1-1, and the consumption of described cilicon oxide filler is 0.25-2.2 weight portion, in terms of solid, the consumption of described water-soluble film-forming resin is 0.8-6.8 weight portion, and the consumption of water is 10-100 weight portion.
Preparation method the most according to claim 2, wherein, described water-soluble silicate relative to 1 weight portion, the consumption of described silane coupler is 1.4-1.8 weight portion, the weight ratio of described first silane coupler and described second silane coupler is 1:0.4-0.6, and the consumption of described cilicon oxide filler is 0.6-0.85 weight portion, in terms of solid, the consumption of described water-soluble film-forming resin is 2.1-2.7 weight portion, and the consumption of water is 25-40 weight portion.
4. according to the preparation method described in any one in claim 1-3, wherein, described first silane coupler is NH2(CH2)2NH(CH2)3Si(OCH3)3、NH2(CH2)2NH(CH2)3Si(OC2H5)3、NH2(CH2)2NH(CH2)3SiCH3(OCH3)2、NH2(CH2)2NHCH2CH(CH3)CH2SiCH3(OCH3)2、HO(CH2)2NH(CH2)2NH(CH2)3SiCH3(OCH3)2、NH2(CH2)2NH(CH2)2NH(CH2)3SiCH3(OCH3)2And NH2(CH2)2NH(CH2)2NH(CH2)3Si(OCH3)3In at least one.
5. according to the preparation method described in any one in claim 1-3, wherein, described second silane coupler is CH2(O)CHCH2O(CH2)3Si(OCH3)3、CH2(O)CHCH2O(CH2)3Si(OC2H5)3、CH2(O)CHCH2O(CH2)3SiCH3(OCH3)2And CH2(O)CHCH2O(CH2)3SiCH3(OC2H5)2In at least one.
6. according to the preparation method described in any one in claim 1-3, wherein, at least one during described water-soluble film-forming resin is water-soluble polyester film-forming resin, soluble epoxide film-forming resin, soluble polyurethane film-forming resin, water-soluble acrylic film-forming resin and water-soluble fluorine carbon film-forming resin.
7. according to the preparation method described in any one in claim 1-3, wherein, at least one during described water-soluble film-forming resin is water-soluble polyester film-forming resin, soluble epoxide film-forming resin, soluble polyurethane film-forming resin, water solublity phenylpropyl alcohol film-forming resin, water-soluble silicon the third film-forming resin and water-soluble fluorine carbon film-forming resin.
Preparation method the most according to claim 7, wherein, described water-soluble silicon the third film-forming resin is Silomer8861 emulsion.
9. according to the preparation method described in any one in claim 1-3, wherein, this preparation method also includes: mixed homogeneously with lubricating auxiliary agent by the material after water and silane coupler mix homogeneously, described lubricating auxiliary agent is one or more in the water-based emulsion of the water-based emulsion of dimethicone, polyether-modified polysiloxanes, the water-based emulsion of Tissuemat E and OPE, relative to the described water-soluble silicate of 1 weight portion, the consumption of described lubricating auxiliary agent is 0.2-1.8 weight portion.
10. the weather resistant application compositions that in claim 1-9, preparation method described in any one prepares.
The weather resistant application compositions described in 11. claim 10 purposes in preparing metal material.
12. 1 kinds of hot-dip metal plated materials, this hot-dip metal plated material includes hot-dip metal plated base material and the coating being attached on this hot-dip metal plated base material, described hot-dip metal plated base material is at least one in galvanizing 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 weather resistant application compositions described in claim 10.
13. hot-dip metal plated materials according to claim 12, wherein, the thickness of described coating is 0.1-1 micron.
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| CN103013337A (en) * | 2011-09-28 | 2013-04-03 | 攀钢集团攀枝花钢铁研究院有限公司 | Metal protective coating and hot galvanizing metal material as well as hot-dip aluminium-zinc metal material |
| CN103031043A (en) * | 2011-09-28 | 2013-04-10 | 攀钢集团攀枝花钢铁研究院有限公司 | Metal protective coating and hot galvanizing metal material and hot dip aluminum-zinc metal material |
| CN103031042A (en) * | 2011-09-28 | 2013-04-10 | 攀钢集团攀枝花钢铁研究院有限公司 | Metal protective coating and hot galvanizing metal material and hot dip aluminum-zinc metal material |
| CN103031061A (en) * | 2011-09-28 | 2013-04-10 | 攀钢集团攀枝花钢铁研究院有限公司 | Metal protective coating and hot galvanizing metal material and hot dip aluminum-zinc metal material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103013337A (en) * | 2011-09-28 | 2013-04-03 | 攀钢集团攀枝花钢铁研究院有限公司 | Metal protective coating and hot galvanizing metal material as well as hot-dip aluminium-zinc metal material |
| CN103031043A (en) * | 2011-09-28 | 2013-04-10 | 攀钢集团攀枝花钢铁研究院有限公司 | Metal protective coating and hot galvanizing metal material and hot dip aluminum-zinc metal material |
| CN103031042A (en) * | 2011-09-28 | 2013-04-10 | 攀钢集团攀枝花钢铁研究院有限公司 | Metal protective coating and hot galvanizing metal material and hot dip aluminum-zinc metal material |
| CN103031061A (en) * | 2011-09-28 | 2013-04-10 | 攀钢集团攀枝花钢铁研究院有限公司 | Metal protective coating and hot galvanizing metal material and hot dip aluminum-zinc metal material |
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