CN104059510B - A kind of chromium and preparation method thereof and hot-dip metal plated material - Google Patents
A kind of chromium and preparation method thereof and hot-dip metal plated material Download PDFInfo
- Publication number
- CN104059510B CN104059510B CN201310400198.8A CN201310400198A CN104059510B CN 104059510 B CN104059510 B CN 104059510B CN 201310400198 A CN201310400198 A CN 201310400198A CN 104059510 B CN104059510 B CN 104059510B
- Authority
- CN
- China
- Prior art keywords
- chromium
- water
- forming resin
- film
- soluble
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The invention provides a kind of chromium, wherein, described chromium contains water, phosphonic acids chelating agent, aluminium dihydrogen phosphate, trivalent chromium source, cilicon oxide filler and water-soluble film-forming resin. Present invention also offers a kind of method preparing chromium. Present invention also offers the chromium prepared according to said method. 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 chromium as above. The coating that the present invention obtains through overcuring at high temperature or has more excellent corrosion resistance after high temperature, and the trivalent chromium in described coating at high temperature will not be changed into Cr VI, complies fully with environmental requirement.
Description
Technical field
The present invention relates to metal protection field, in particular it relates to a kind of chromium, a kind of prepare the method for chromium, the method chromium obtained and the hot-dip metal plated material of one.
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 apply layer of metal protective coating to form protecting film on the surface of hot-dip metal plated material. Thus the performance of metal protection coating is particularly significant for the anti-corrosion of hot-dip metal plated material.
Using the coating containing chromium to form protecting film on the surface of hot-dip metal plated material is a kind of important selection, has bigger market share. But, parliament of European Union and council passed through " the Restriction of the Use of Certain Hazardous Substances in Electrical and Electronic Equipment " on February 13rd, 2003, were called for short RoHS instruction, i.e. European Union's 2002/95/EC instruction. In the electronic and electrical equipment that this command request was newly put on market after on July 1st, 2006, the material being prevented or restricted from using has lead (Pb), hydrargyrum (Hg), cadmium (Cd), Cr VI (Cr6+). Wherein, plumbous (Pb), Cr VI (Cr6+), cadmium (Cd), hydrargyrum (Hg) belong to the steel plate composition or Coating composition or coating composition that limit.
Therefore, at home and abroad in market, the use of chromyl coating is greatly limited, and at present, the developing focus of metal protection coating transfers to not chromyl environment-friendly type coating, particularly chromium.
Such as, CN102477551A discloses a kind of surface conditioning agent, falls within a kind of chromium, and this chromium contains styrene-acrylic emulsion and/or silicone acrylic emulsion, fluorine carbon emulsion and/or fluoro-silicone emulsion, trivalent chromium compound and phosphate.
But it is demonstrated experimentally that the corrosion resistance of the protecting film of this chromium formation is still relatively low.
Summary of the invention
For the defect that the corrosion resistance overcoming protecting film that existing chromium formed is still relatively low, the invention provides a kind of chromium, a kind of prepare the method for chromium, the method chromium obtained and the hot-dip metal plated material of one.
On the one hand, the invention provides a kind of chromium, wherein, described chromium contains water, phosphonic acids chelating agent, aluminium dihydrogen phosphate, trivalent chromium source, cilicon oxide filler and water-soluble film-forming resin.
On the other hand, present invention also offers a kind of method preparing chromium, wherein, the method includes: (1) prepares the first solution, and described first solution contains phosphonic acids chelating agent and aluminium dihydrogen phosphate; (2) preparing the second solution, described second solution contains trivalent chromium source, nano silicon, water-soluble film-forming resin; (3) by described first solution and the second solution mix homogeneously.
On the other hand, present invention also offers the chromium prepared according to said method.
On the other hand, 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 chromium as above.
By technique scheme, the coating that the present invention obtains through overcuring at high temperature or has more excellent corrosion resistance after high temperature, and the trivalent chromium in described coating at high temperature will not be changed into Cr VI, complies fully with environmental requirement. Additionally, the storage endurance of chromium provided by the invention is very 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 specific embodiment 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.
In the present invention, when illustrating on the contrary, the volume of gas and liquid is at 20 DEG C, the numerical value of a standard atmosphere pressure. In the present invention, when not making contrary explanation, the scope of the term " solution " used is not limited to the particle diameter of the dispersate disperse system (true solution) less than 1nm, but refers to homogeneous liquefied mixture, it is possible to include colloidal dispersion (colloid solution).
On the one hand, the invention provides a kind of chromium, wherein, described chromium contains water, phosphonic acids chelating agent, aluminium dihydrogen phosphate, trivalent chromium source, cilicon oxide filler and water-soluble film-forming resin.
Wherein, in described chromium, the content of phosphonic acids chelating agent is 3-18g/L, it is preferred to 5-15g/L.
Further, in described chromium, relative to the phosphonic acids chelating agent of every weight portion, the content of aluminium dihydrogen phosphate can be 0.5-6 weight portion, it is preferred to 1-3 weight portion.
In described chromium, relative to the phosphonic acids chelating agent of every weight portion, with the cubage of chromium element, the content in trivalent chromium source can be 0.25-1.6 weight portion, it is preferred to 0.5-1 weight portion.
In described chromium, relative to the phosphonic acids chelating agent of every weight portion, the content of cilicon oxide filler can be 3-8 weight portion, it is preferred to 4.5-6.5 weight portion.
In described chromium, relative to the phosphonic acids chelating agent of every weight portion, the content of water-soluble film-forming resin can be 3-10 weight portion; It is preferably 5.5-7.5 weight portion.
In order to improve the performance of the coating that described chromium is formed further, under preferable case, in described chromium, the content of phosphonic acids chelating agent is 5-15g/L, and, phosphonic acids chelating agent relative to every weight portion, the content of aluminium dihydrogen phosphate is 1-3 weight portion, and with the cubage of chromium element, the content in trivalent chromium source is 0.5-1 weight portion, the content of cilicon oxide filler is 4.5-6.5 weight portion, and the content of water-soluble film-forming resin is 5.5-7.5 weight portion.
In the present invention, described phosphonic acids chelating agent can be various can complexation bivalence and/or trivalent metal cation containing phosphonic acids material. In order to improve the performance of the coating that described chromium is formed further; under preferable case; described phosphonic acids chelating agent is 2-phosphonobutane-1; 2; 4-tricarboxylic acids, 2-phosphonobutane-1; at least one in the alkali metal salt of 2,4-tricarboxylic alkali metal salts, 2-HPAA and 2-HPAA.
Wherein, described trivalent chromium source can be Cr (OH)3, chromic sulfate, chromic nitrate, chromium phosphate, biphosphate chromium, chromium trichloride, chromium acetate, chromic tartrate, chromium+oxalic acid, chromium citrate, at least one in chromium gluconate and maleic acid chromium.
In the present invention, described cilicon oxide filler does not have special requirement, it is possible to for the various fillers based on silicon oxide, for instance, 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, it is 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 content of cilicon oxide filler and/or consumption are to calculate with the weight of silicon oxide itself, the consumption of such as nano silicon dioxide sol is to calculate with the gauge of the silicon dioxide in colloidal sol, the numerical computations obtained after being namely multiplied by its dioxide-containing silica percent (weight) with the weight of nano silicon dioxide sol.
In the present invention, 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 not special requirement of the present invention, as long as can be used in film forming, 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 polyester resin of trade mark CB2200), the water solublity phenylpropyl alcohol film-forming resin (water-soluble film-forming resin namely obtained by styrene monomer and acrylic acid (ester) class monomer polymerization, 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 (the water-soluble film-forming resin namely obtained by the monomer polymerization containing epoxy radicals, such as purchased from Dongguan City Heima Chemical Co., Ltd., the trade mark is the epoxy resin of BH620), soluble polyurethane 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 polyurethane resin of the trade mark 812), water-soluble silicon the third film-forming resin (water-soluble film-forming resin namely obtained by silicone based monomer and acrylic acid (ester) class monomer polymerization, 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 (the water-soluble film-forming resin namely obtained by acrylic acid (ester) class monomer polymerization, such as purchased from the acrylic resin that the trade mark is A-3418 of Guangzhou Ou Peng chemical industry) 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 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 described water-soluble film-forming resin is water solublity phenylpropyl alcohol film-forming resin and/or water-soluble fluorine carbon film-forming resin. The content of water-soluble film-forming resin and/or consumption calculate with solid. Herein solid be used for calculating or representing that the solid implication of solid content is identical, be water-soluble film-forming resin and remove remaining composition after solvent.
Wherein, it is preferable that in situation, described chromium is possibly together with sodium phosphate, and relative to the phosphonic acids chelating agent of every weight portion, the content of sodium phosphate is 0.5-4 weight portion, more preferably 1-2 weight portion; Further, described trivalent chromium source is obtained by reducing agent reduction of hexavalent chromium compound. Specifically, it is possible to the method in reference literature CN101608073B prepares trivalent chromium source.
On the other hand, present invention also offers a kind of method preparing chromium, wherein, the method includes: (1) prepares the first solution, and described first solution contains phosphonic acids chelating agent and aluminium dihydrogen phosphate; (2) preparing the second solution, described second solution contains trivalent chromium source, nano silicon, water-soluble film-forming resin; (3) by described first solution and the second solution mix homogeneously.
Wherein, in the method, relative to the phosphonic acids chelating agent of every weight portion, the consumption of aluminium dihydrogen phosphate can be 0.5-6 weight portion, it is preferred to 1-3 weight portion.
Wherein, in the method, relative to the phosphonic acids chelating agent of every weight portion, with the cubage of chromium element, the consumption in trivalent chromium source can be 0.25-1.6 weight portion, it is preferred to 0.5-1 weight portion.
Wherein, in the method, relative to the phosphonic acids chelating agent of every weight portion, the consumption of cilicon oxide filler can be 3-8 weight portion, it is preferred to 4.5-6.5 weight portion.
Wherein, in the method, relative to the phosphonic acids chelating agent of every weight portion, the consumption of water-soluble film-forming resin can be 3-10 weight portion; It is preferably 5.5-7.5 weight portion.
Wherein, in the method, it is possible to the consumption making the phosphonic acids chelating agent in chromium by regulating the addition of water is 3-18g/L; It is preferably 5-15g/L. At least one in the mixture of the first solution, the second solution and the first solution and the second solution can be selected to regulate the addition of water.
Under preferable case, in the first solution, the content of phosphonic acids chelating agent is 10-30 weight %. Under preferable case, in the second solution, the content in trivalent chromium source is 0.07-3 weight %.
In order to improve the performance of the coating that described chromium is formed further, under preferable case, phosphonic acids chelating agent relative to every weight portion, the consumption of aluminium dihydrogen phosphate is 1-3 weight portion, and with the cubage of chromium element, the consumption in trivalent chromium source is 0.5-1 weight portion, the consumption of cilicon oxide filler is 4.5-6.5 weight portion, the consumption of water-soluble film-forming resin is 5.5-7.5 weight portion, and, the content making the phosphonic acids chelating agent in chromium by regulating the addition of water is 5-15g/L.
In the present invention, described phosphonic acids chelating agent can be various can complexation bivalence and/or trivalent metal cation containing phosphonic acids material, for instance, PAPE (PAPE). In order to improve the performance of the coating that described chromium is formed further; under preferable case; described phosphonic acids chelating agent is 2-phosphonobutane-1; 2; 4-tricarboxylic acids (i.e. PBTCA), 2-phosphonobutane-1; at least one in the alkali metal salt of 2,4-tricarboxylic alkali metal salts, 2-HPAA (i.e. HPAA) and 2-HPAA.
Wherein, described trivalent chromium source can be Cr (OH)3, chromic sulfate, chromic nitrate, chromium phosphate, biphosphate chromium, chromium trichloride, chromium acetate, chromic tartrate, chromium+oxalic acid, chromium citrate, at least one in chromium gluconate and maleic acid chromium.
In the present invention, described cilicon oxide filler does not have special requirement, it is possible to for the various fillers based on silicon oxide, for instance, 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, it is 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 content of cilicon oxide filler and/or consumption are to calculate with the weight of silicon oxide itself, the consumption of such as nano silicon dioxide sol is to calculate with the gauge of the silicon dioxide in colloidal sol, the numerical computations obtained after being namely multiplied by its dioxide-containing silica percent (weight) with the weight of nano silicon dioxide sol.
In the present invention, 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 not special requirement of the present invention, as long as can be used in film forming, 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 polyester resin of trade mark CB2200), the water solublity phenylpropyl alcohol film-forming resin (water-soluble film-forming resin namely obtained by styrene monomer and acrylic acid (ester) class monomer polymerization, 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 (the water-soluble film-forming resin namely obtained by the monomer polymerization containing epoxy radicals, such as purchased from Dongguan City Heima Chemical Co., Ltd., the trade mark is the epoxy resin of BH620), soluble polyurethane 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 polyurethane resin of the trade mark 812), water-soluble silicon the third film-forming resin (water-soluble film-forming resin namely obtained by silicone based monomer and acrylic acid (ester) class monomer polymerization, 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 (the water-soluble film-forming resin namely obtained by acrylic acid (ester) class monomer polymerization, such as purchased from the acrylic resin that the trade mark is A-3418 of Guangzhou Ou Peng chemical industry) 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 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 described water-soluble film-forming resin is water solublity phenylpropyl alcohol film-forming resin and/or water-soluble fluorine carbon film-forming resin. The content of water-soluble film-forming resin and/or consumption calculate with solid. Herein solid be used for calculating or representing that the solid implication of solid content is identical, be water-soluble film-forming resin and remove remaining composition after solvent.
Wherein, it is preferable that in situation, described second solution also has sodium phosphate, and relative to the phosphonic acids chelating agent of every weight portion, the consumption of sodium phosphate is 0.5-4 weight portion, it is preferred to 1-2 weight portion; Further, described trivalent chromium source is obtained by reducing agent reduction of hexavalent chromium compound. Specifically, it is possible to the method in reference literature CN101608073B prepares trivalent chromium source. When obtaining trivalent chromium source by reducing agent reduction of hexavalent chromium compound, the amount in trivalent chromium source calculates with hexavalent chromium compound.
On the other hand, present invention also offers the chromium prepared according to said method.
On the other hand, 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 chromium as above.
Wherein, the thickness of described coating can be the known thickness of passivating film on zinc-plating material, and the present invention has no particular limits, and overweight coating then tack declines, and cover light then corrosion resistance declines, it is thus preferred in situation, the thickness of described coating is 0.1-1 micron.
Wherein, the method adhering to described coating on zinc-plated base material includes being attached on zinc-plated base material described surface conditioning agent, then dries, and dry temperature can be 60-120 DEG C, and the time can be the 0.5-3 second.
In order to make the thickness of described coating meet above-mentioned requirement, the described surface conditioning agent consumption that makes on the zinc-plated base material of unit are can correspondingly adjust, such as when the thickness requiring described coating is 0.5-1.5 micron, the zinc-plated substrate surface of every square metre relatively, the consumption of described surface conditioning agent can be 0.2-1.5g.
In the present invention, the volume of all liq and gas refers both to 20 DEG C, the volume of 1 standard atmosphere pressure.
In the present invention, the solid content of various organic binders and viscosity and respectively according to the method measurement of standard GB/T/T2793 and GB/T1723 regulation and record.
Hereinafter will be described the present invention by embodiment, but the scope of the present invention will be not limited in embodiment.
Preparation embodiment 1
This is prepared embodiment and obtains trivalent chromium source for the method illustrating in reference literature CN101608073B by reducing agent reduction of hexavalent chromium compound.
The enamel reaction still of 3000 liters adds 300 kilograms of deionized waters, adds 50 kilograms of chromic anhydride (CrO3), the agitator starting reactor stirs 10 minutes, makes chromic anhydride dissolve. After chromic anhydride is completely dissolved, at room temperature add the citric acid of double centner, start rapidly agitator, make citric acid rapid solution. When solution does not emit bubble, judge that reaction completes, and obtains required trivalent chromium source.
Embodiment 1
By phosphonic acids chelating agent (2-phosphonobutane-1,2, the 4-tricarboxylic acids of 10g, purchased from Shandong Taihe Water Treatment Co., Ltd., numbering CASNo.37971-36-1) and the aluminium dihydrogen phosphate of 20g add in 20g water, under the mixing speed of 1500 revs/min, mixing is to uniformly, obtains the first solution.
By (the trivalent chromium source that preparation embodiment 1 prepares, trivalent chromium source of 7g, addition is calculated with the gauge of chromium element), cilicon oxide filler (the nano silicon dioxide sol of 56g, purchased from Shandong Bai Te new material company limited, the trade mark is SS-30, addition is in silicon dioxide), the water-soluble film-forming resin of 65g is (by the styrene-acrylic emulsion of equivalent (purchased from Guangzhou Chao Long Chemical Industry Science Co., Ltd, the trade mark is xy-108b styrene-acrylic emulsion, solid content is 48 weight %, viscosity is that 500-1000mPa s) and fluorine carbon emulsion are (purchased from Beijing Shouchuang Nano Techn Co., Ltd., the trade mark is the water-base fluorocarbon emulsion of SKFT-I, solid content is 45 weight %, viscosity be 500-1000mPa s) composition) and 15g sodium phosphate addition 585g water in, under the mixing speed of 1500 revs/min, mixing is to uniformly, obtain the second solution.
Merging the first solution and the second solution, and be 1L with water adjustment volume, under the mixing speed of 1500 revs/min, mixing is to uniformly, obtains uniform liquid. This uniform liquid is the chromium of the present embodiment.
Embodiment 2
By phosphonic acids chelating agent (the 2-HPAA of 10g; purchased from Shandong Taihe Water Treatment Co., Ltd.; numbering CASNo.23783-26-8) and the aluminium dihydrogen phosphate of 10g add in 30g water, under the mixing speed of 1500 revs/min, mixing is to uniformly, obtains the first solution.
By (the trivalent chromium source that preparation embodiment 1 prepares, trivalent chromium source of 5g, addition is calculated with the gauge of chromium element), cilicon oxide filler (the nano silicon dioxide sol of 65g, purchased from Shandong Bai Te new material company limited, the trade mark is SS-30, addition is in silicon dioxide), (fluorine carbon emulsion is (purchased from Beijing Shouchuang Nano Techn Co., Ltd. for the water-soluble film-forming resin of 75g, the trade mark is the water-base fluorocarbon emulsion of SKFT-I, solid content is 45 weight %, viscosity is 500-1000mPa s)) and 10g sodium phosphate add in 570g water, under the mixing speed of 1500 revs/min, mixing is to uniformly, obtain the second solution.
Merging the first solution and the second solution, and be 1L with water adjustment volume, under the mixing speed of 1500 revs/min, mixing is to uniformly, obtains uniform liquid. This uniform liquid is the chromium of the present embodiment.
Embodiment 3
By phosphonic acids chelating agent (2-phosphonobutane-1,2,4-tricarboxylic acids four sodium of 10g, purchased from Shandong Taihe Water Treatment Co., Ltd., be numbered CASNo.40372-66-5) and the aluminium dihydrogen phosphate of 30g add in 30g water, under the mixing speed of 1500 revs/min, mixing is to uniformly, obtains the first solution.
By (the trivalent chromium source that preparation embodiment 1 prepares, trivalent chromium source of 10g, addition is calculated with the gauge of chromium element), cilicon oxide filler (the nano silicon dioxide sol of 45g, purchased from Shandong Bai Te new material company limited, the trade mark is SS-30, addition is in silicon dioxide), (styrene-acrylic emulsion is (purchased from Guangzhou Chao Long Chemical Industry Science Co., Ltd for the water-soluble film-forming resin of 55g, the trade mark is xy-108b styrene-acrylic emulsion, solid content is 48 weight %, viscosity is 500-1000mPa s)) and 20g sodium phosphate add in 595g water, under the mixing speed of 1500 revs/min, mixing is to uniformly, obtain the second solution.
Merging the first solution and the second solution, and be 1L with water adjustment volume, under the mixing speed of 1500 revs/min, mixing is to uniformly, obtains uniform liquid. This uniform liquid is the chromium of the present embodiment.
Embodiment 4
By phosphonic acids chelating agent (2-phosphonobutane-1,2, the 4-tricarboxylic acids of 10g, purchased from Shandong Taihe Water Treatment Co., Ltd., numbering CASNo.37971-36-1) and the aluminium dihydrogen phosphate of 20g add in 20g water, under the mixing speed of 1500 revs/min, mixing is to uniformly, obtains the first solution.
By trivalent chromium source (the biphosphate chromium of 7g, addition is calculated with the gauge of chromium element), cilicon oxide filler (the nano silicon dioxide sol of 56g, purchased from Shandong Bai Te new material company limited, the trade mark is SS-30, addition is in silicon dioxide), the water-soluble film-forming resin of 65g is (by the styrene-acrylic emulsion of equivalent (purchased from Guangzhou Chao Long Chemical Industry Science Co., Ltd, the trade mark is xy-108b styrene-acrylic emulsion, solid content is 48 weight %, viscosity is that 500-1000mPa s) and fluorine carbon emulsion are (purchased from Beijing Shouchuang Nano Techn Co., Ltd., the trade mark is the water-base fluorocarbon emulsion of SKFT-I, solid content is 45 weight %, viscosity is 500-1000mPa s) composition) add in 600g water, under the mixing speed of 1500 revs/min, mixing is to uniformly, obtain the second solution.
Merging the first solution and the second solution, and be 1L with water adjustment volume, under the mixing speed of 1500 revs/min, mixing is to uniformly, obtains uniform liquid. This uniform liquid is the chromium of the present embodiment.
Embodiment 5
By phosphonic acids chelating agent (2-phosphonobutane-1,2, the 4-tricarboxylic acids of 10g, purchased from Shandong Taihe Water Treatment Co., Ltd., numbering CASNo.37971-36-1) and the aluminium dihydrogen phosphate of 60g add in 60g water, under the mixing speed of 1500 revs/min, mixing is to uniformly, obtains the first solution.
By (the trivalent chromium source that preparation embodiment 1 prepares, trivalent chromium source of 16g, addition is calculated with the gauge of chromium element), cilicon oxide filler (the nano silicon dioxide sol of 30g, purchased from Shandong Bai Te new material company limited, the trade mark is SS-30, addition is in silicon dioxide), the water-soluble film-forming resin of 30g is (by the styrene-acrylic emulsion of equivalent (purchased from Guangzhou Chao Long Chemical Industry Science Co., Ltd, the trade mark is xy-108b styrene-acrylic emulsion, solid content is 48 weight %, viscosity is that 500-1000mPa s) and fluorine carbon emulsion are (purchased from Beijing Shouchuang Nano Techn Co., Ltd., the trade mark is the water-base fluorocarbon emulsion of SKFT-I, solid content is 45 weight %, viscosity be 500-1000mPa s) composition) and 15g sodium phosphate addition 560g water in, under the mixing speed of 1500 revs/min, mixing is to uniformly, obtain the second solution.
Merging the first solution and the second solution, and be 1L with water adjustment volume, under the mixing speed of 1500 revs/min, mixing is to uniformly, obtains uniform liquid. This uniform liquid is the chromium of the present embodiment.
Embodiment 6
By phosphonic acids chelating agent (2-phosphonobutane-1,2, the 4-tricarboxylic acids of 10g, purchased from Shandong Taihe Water Treatment Co., Ltd., numbering CASNo.37971-36-1) and the aluminium dihydrogen phosphate of 5g add in 20g water, under the mixing speed of 1500 revs/min, mixing is to uniformly, obtains the first solution.
By (the trivalent chromium source that preparation embodiment 1 prepares, trivalent chromium source of 2.5g, addition is calculated with the gauge of chromium element), cilicon oxide filler (the nano silicon dioxide sol of 80g, purchased from Shandong Bai Te new material company limited, the trade mark is SS-30, addition is in silicon dioxide), the water-soluble film-forming resin of 100g is (by the styrene-acrylic emulsion of equivalent (purchased from Guangzhou Chao Long Chemical Industry Science Co., Ltd, the trade mark is xy-108b styrene-acrylic emulsion, solid content is 48 weight %, viscosity is that 500-1000mPa s) and fluorine carbon emulsion are (purchased from Beijing Shouchuang Nano Techn Co., Ltd., the trade mark is the water-base fluorocarbon emulsion of SKFT-I, solid content is 45 weight %, viscosity be 500-1000mPa s) composition) and 15g sodium phosphate addition 545g water in, under the mixing speed of 1500 revs/min, mixing is to uniformly, obtain the second solution.
Merging the first solution and the second solution, and be 1L with water adjustment volume, under the mixing speed of 1500 revs/min, mixing is to uniformly, obtains uniform liquid. This uniform liquid is the chromium of the present embodiment.
Embodiment 7
Chromium is prepared according to the method for embodiment 1, the difference is that, use PAPE (PAPE, purchased from Shandong Taihe Water Treatment Co., Ltd.) as phosphonic acids chelating agent.
Comparative example 1
Chromium is prepared according to the method for embodiment 1, the difference is that, phosphonic acids chelating agent is replaced with phytic acid.
Preparation embodiment 2
The chromium that Example 1-7 and comparative example 1 obtain is respectively applied in galvanized steel plain sheet (purchased from Pangang Group Panzhihua Steel Vanadium Co., Ltd., model DX54D, containing zinc 95 weight % 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, this prepares the chromium used in embodiment is all stored the chromium of 1 day after having prepared (namely obtaining uniform liquid).
Preparation embodiment 3-5
Galvanized steel plain sheet after processing according to the method preparation of preparation embodiment 2, the difference is that, the chromium of use is all stored the chromium of 60,120 and 180 days after having prepared (namely obtaining uniform liquid).
Testing example 1
By the requirement of regulation in GB/T101251997, carry out neutral salt spray test, measure the corrosion resisting property after the galvanized steel plain sheet after the process of preparation embodiment 2-5 toasts 30s at 400 DEG C respectively. It is qualified to be considered as by " salt spray test 144h, corrosion area < 3% ".
Test result as above is as shown in table 1. Natural law in bracket represents the storage time of chromium.
According to GB21275-2007 " in electronic and electrical equipment regulated substance Cr VI detection method " the standard testing content of 6-valence Cr ions specified, result is listed in table 1(and only lists), it is qualified that namely content of 6-valence Cr ions is considered as lower than 2ppm.
Table 1
From the data of table 1 it can be seen that the corrosion resistance of the protecting film of chromium provided by the invention formation is very excellent, and the storage endurance of chromium provided by the invention is also very excellent. And, data according to table 1 are visible, content at preferred phosphonic acids chelating agent is 5-15g/L, and, relative to the phosphonic acids chelating agent of every weight portion, the content of aluminium dihydrogen phosphate is 1-3 weight portion, with the cubage of chromium element, the content in trivalent chromium source is 0.5-1 weight portion, and the content of cilicon oxide filler is 4.5-6.5 weight portion, when the content of water-soluble film-forming resin is 5.5-7.5 weight portion, it is possible to improve the corrosion resistance of the protecting film that described chromium is formed further. And; data according to table 1 are visible; it is 2-phosphonobutane-1 at preferred described phosphonic acids chelating agent; 2; 4-tricarboxylic acids, 2-phosphonobutane-1; when at least one in the alkali metal salt of 2,4-tricarboxylic alkali metal salts, 2-HPAA and 2-HPAA, it is possible to improve the corrosion resistance of the protecting film that described chromium 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 being 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 reconcilable situation, it is possible to be combined by any suitable mode, in order to avoid unnecessary repetition, various possible compound modes are no longer illustrated by the present invention 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 (10)
1. a chromium, it is characterized in that, described chromium contains water, phosphonic acids chelating agent, aluminium dihydrogen phosphate, trivalent chromium source, cilicon oxide filler, water-soluble film-forming resin and sodium phosphate, described phosphonic acids chelating agent is 2-phosphonobutane-1, 2, 4-tricarboxylic acids four sodium, the content of phosphonic acids chelating agent is 5-15g/L, and, phosphonic acids chelating agent relative to every weight portion, the content of aluminium dihydrogen phosphate is 1-3 weight portion, cubage with chromium element, the content in trivalent chromium source is 0.5-1 weight portion, the content of cilicon oxide filler is 4.5-6.5 weight portion, the content of water-soluble film-forming resin is 5.5-7.5 weight portion, the content of sodium phosphate is 0.5-4 weight portion.
2. chromium according to claim 1, wherein,
Described trivalent chromium source is Cr (OH)3, chromic sulfate, chromic nitrate, chromium phosphate, biphosphate chromium, chromium trichloride, chromium acetate, chromic tartrate, chromium+oxalic acid, chromium citrate, at least one in chromium gluconate and maleic acid chromium;
Described cilicon oxide filler is nano-silica powder and/or nano silicon dioxide sol;
Described water-soluble film-forming resin is at least one in water-soluble polyester film-forming resin, water solublity phenylpropyl alcohol film-forming resin, soluble epoxide film-forming resin, soluble polyurethane film-forming resin, water-soluble silicon the third film-forming resin, water-soluble acrylic film-forming resin and water-soluble fluorine carbon film-forming resin.
3. chromium according to claim 1, wherein, described trivalent chromium source is obtained by reducing agent reduction of hexavalent chromium compound.
4. chromium according to claim 1, wherein, relative to the phosphonic acids chelating agent of every weight portion, the content of sodium phosphate is 1-2 weight portion.
5. the method preparing chromium, it is characterised in that the method includes:
(1) preparing the first solution, described first solution contains phosphonic acids chelating agent and aluminium dihydrogen phosphate;
(2) preparing the second solution, described second solution contains trivalent chromium source, nano silicon, water-soluble film-forming resin;
(3) by described first solution and the second solution mix homogeneously;
Described second solution contains sodium phosphate, described phosphonic acids chelating agent is 2-phosphonobutane-1,2,4-tricarboxylic acids four sodium, phosphonic acids chelating agent relative to every weight portion, the consumption of aluminium dihydrogen phosphate is 1-3 weight portion, cubage with chromium element, the consumption in trivalent chromium source is 0.5-1 weight portion, the consumption of cilicon oxide filler is 4.5-6.5 weight portion, and the consumption of water-soluble film-forming resin is 5.5-7.5 weight portion, and the consumption of sodium phosphate is 0.5-4 weight portion, further, the content making the phosphonic acids chelating agent in chromium by regulating the addition of water is 5-15g/L.
6. method according to claim 5, wherein,
Described trivalent chromium source is Cr (OH)3, chromic sulfate, chromic nitrate, chromium phosphate, biphosphate chromium, chromium trichloride, chromium acetate, chromic tartrate, chromium+oxalic acid, chromium citrate, at least one in chromium gluconate and maleic acid chromium;
Described cilicon oxide filler is nano-silica powder and/or nano silicon dioxide sol;
Described water-soluble film-forming resin is at least one in water-soluble polyester film-forming resin, water solublity phenylpropyl alcohol film-forming resin, soluble epoxide film-forming resin, soluble polyurethane film-forming resin, water-soluble silicon the third film-forming resin, water-soluble acrylic film-forming resin and water-soluble fluorine carbon film-forming resin.
7. method according to claim 5, wherein, described trivalent chromium source is obtained by reducing agent reduction of hexavalent chromium compound.
8. method according to claim 5, wherein, relative to the phosphonic acids chelating agent of every weight portion, the consumption of sodium phosphate is 1-2 weight portion.
9. the chromium that in claim 5-8, method described in any one prepares.
10. a 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 the chromium in claim 1-4 and 9 described in any one.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310400198.8A CN104059510B (en) | 2013-09-05 | 2013-09-05 | A kind of chromium and preparation method thereof and hot-dip metal plated material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310400198.8A CN104059510B (en) | 2013-09-05 | 2013-09-05 | A kind of chromium and preparation method thereof and hot-dip metal plated material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104059510A CN104059510A (en) | 2014-09-24 |
| CN104059510B true CN104059510B (en) | 2016-06-15 |
Family
ID=51547450
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310400198.8A Expired - Fee Related CN104059510B (en) | 2013-09-05 | 2013-09-05 | A kind of chromium and preparation method thereof and hot-dip metal plated material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104059510B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107815194A (en) * | 2017-11-17 | 2018-03-20 | 湖南太子化工涂料有限公司 | A kind of galvanized sheet coating |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1503858A (en) * | 2000-09-07 | 2004-06-09 | �ձ�������ʽ���� | Hexavalent chromium-free suface-treating agent for sn-or al-based coated steel sheet and surface treated steel sheet |
-
2013
- 2013-09-05 CN CN201310400198.8A patent/CN104059510B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1503858A (en) * | 2000-09-07 | 2004-06-09 | �ձ�������ʽ���� | Hexavalent chromium-free suface-treating agent for sn-or al-based coated steel sheet and surface treated steel sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104059510A (en) | 2014-09-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104060250B (en) | A kind of chromium ion passivating solution and preparation method thereof and hot-dip metal plated material | |
| CN104060249B (en) | Metal surface chromium inorganic agent and preparation method thereof and hot-dip metal plated material | |
| CN103360820B (en) | A kind of metal protection coating and uses thereof and hot-dip metal plated material | |
| CN104059495B (en) | Chromium-free passivation liquid and its production and use and metal material | |
| CN104073074B (en) | A kind of metal surface chromium inorganic agent and preparation method thereof and hot-dip metal plated material | |
| CN104060251B (en) | Chromium ion passivating solution and preparation method thereof and hot-dip metal plated material | |
| CN104060252B (en) | Surface conditioning agent and preparation method thereof and hot-dip metal plated material | |
| CN104073075B (en) | A kind of chromium and preparation method thereof and hot-dip metal plated material | |
| CN104059509B (en) | Metal inactivating solution and preparation method thereof and hot-dip metal plated material | |
| CN103360818B (en) | A kind of metal protection coating and uses thereof and hot-dip metal plated material | |
| CN104059510B (en) | A kind of chromium and preparation method thereof and hot-dip metal plated material | |
| CN103360841B (en) | A kind of metal protection coating and uses thereof and hot-dip metal plated material | |
| CN103360812B (en) | A kind of metal protection coating and uses thereof and hot-dip metal plated material | |
| CN103360811B (en) | A kind of metal protection coating and uses thereof and hot-dip metal plated material | |
| CN103360837B (en) | A kind of metal protection coating and uses thereof and hot-dip metal plated material | |
| CN103360819B (en) | A kind of metal protection coating and uses thereof and hot-dip metal plated material | |
| CN103360845B (en) | A kind of metal protection coating and uses thereof and hot-dip metal plated material | |
| CN103360827B (en) | A kind of metal protection coating and uses thereof and hot-dip metal plated material | |
| CN103360823B (en) | A kind of metal protection coating and uses thereof and hot-dip metal plated material | |
| CN103360840B (en) | A kind of metal protection coating and uses thereof and hot-dip metal plated material | |
| CN103360821B (en) | A kind of metal protection coating and uses thereof and hot-dip metal plated material | |
| CN103360842B (en) | A kind of metal protection coating and uses thereof and hot-dip metal plated material | |
| CN103360815B (en) | A kind of metal protection coating and uses thereof and hot-dip metal plated material | |
| CN103360843B (en) | A kind of metal protection coating and uses thereof and hot-dip metal plated material | |
| CN103360914B (en) | A kind of metal protection coating and uses thereof and hot-dip metal plated material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160615 Termination date: 20170905 |