CN104073074A - Metal surface chromium treating agent, preparation method thereof and hot-dip metal material - Google Patents
Metal surface chromium treating agent, preparation method thereof and hot-dip metal material Download PDFInfo
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Abstract
The invention provides a metal surface chromium treating agent. The metal surface chromium treating agent contain water, a phosphonic acid complexing agents, a polycarboxylic acid water-based dispersing agent, aluminium dihydrogen phosphate, a trivalent chromium source, silicon oxide fillers and water-soluble film-forming resin, wherein the phosphonic acid complexing agents are amino trimethylene phosphonic acid and/or alkali metal salts of amino trimethylene phosphonic acid. The invention also provides a method for preparing the metal surface chromium treating agent and a hot-dip metal material. The hot-dip metal material comprises a hot-dip metal substrate and a coating adhered to the hot-dip metal substrate, wherein the coating is a curing product of the metal surface chromium treating agent. The coating obtained through curing has excellent corrosion resistance at or after high temperature. Trivalent chromium in the coating cannot be turned into hexavalent chromium at high temperature, so that the coating absolutely meets the environment-friendly requirements.
Description
Technical field
The present invention relates to metal protection field, particularly, relate to a kind of metallic surface chromium treatment agent, a kind of metallic surface chromium treatment agent of preparing the method for metallic surface chromium treatment agent, obtained by the method and a kind of hot-dip metal plated material.
Background technology
Hot-dip metal plated material, comprises hot-dip galvanized metal material and hot-dip aluminizing zinc metallic substance, in order to prevent corrosion, and all can be at the surface of hot-dip metal plated material coating layer of metal protective coating to form protective film.Thereby the performance of metal protection coating is very important for the rust protection of hot-dip metal plated material.
Using and forming protective film containing the coating of chromium on the surface of hot-dip metal plated material is a kind of important selection, has larger share of market.But parliament of European Union and board of management have passed through " the Restriction of the Use of Certain Hazardous Substances in Electrical and Electronic Equipment " on February 13rd, 2003, be called for short RoHS instruction, i.e. the 2002/95/EC of European Union instruction.In this command request later electronic and electrical equipment of newly putting on market on July 1st, 2006, forbid or limit the material using have lead (Pb), mercury (Hg), cadmium (Cd), sexavalent chrome (Cr
6+).Wherein, plumbous (Pb), sexavalent chrome (Cr
6+), cadmium (Cd), mercury (Hg) belong to the steel plate composition or Coating composition or the coated component 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 is transferred to not chromyl environment-friendly type coating, particularly trivalent chromic ion coating.
For example, CN102477551A discloses a kind of surface treatment agent, also belongs to a kind of trivalent chromic ion coating, and this trivalent chromic ion coating contains benzene emulsion and/or organosilicon crylic acid latex, fluorine carbon emulsion and/or fluoro-silicone emulsion, trivalent chromium compound and phosphoric acid salt.
But the solidity to corrosion that experiment showed, the protective film that this trivalent chromic ion coating forms is still lower.
Summary of the invention
For the solidity to corrosion that overcomes the protective film that existing metallic surface chromium treatment agent forms still lower defect, the invention provides a kind of metallic surface chromium treatment agent, a kind of metallic surface chromium treatment agent of preparing the method for metallic surface chromium treatment agent, obtained by the method and a kind of hot-dip metal plated material.
On the one hand, the invention provides a kind of metallic surface chromium treatment agent, wherein, described metallic surface chromium treatment agent contains water, phosphonic acids complexing agent, poly carboxylic acid aqueous dispersant, aluminium dihydrogen phosphate, trivalent chromium source, cilicon oxide filler and water-soluble film-forming resin; Described phosphonic acids complexing agent is an alkali metal salt of Amino Trimethylene Phosphonic Acid and/or Amino Trimethylene Phosphonic Acid.
On the other hand, the present invention also provides a kind of method of preparing metallic surface chromium treatment agent, and wherein, the method comprises: (1) prepares the first solution, and described the first solution contains phosphonic acids complexing agent, poly carboxylic acid aqueous dispersant and aluminium dihydrogen phosphate; Described phosphonic acids complexing agent is an alkali metal salt of Amino Trimethylene Phosphonic Acid and/or Amino Trimethylene Phosphonic Acid; (2) prepare the second solution, described the second solution contains trivalent chromium source, nano silicon, water-soluble film-forming resin; (3) described the first solution and the second solution are mixed.
On the other hand, the present invention also provides the metallic surface preparing according to aforesaid method chromium treatment agent.
On the other hand, the present invention also provides a kind of hot-dip metal plated material, this hot-dip metal plated material comprises hot-dip metal plated base material and is attached to the coating on this hot-dip metal plated base material, described hot-dip metal plated base material is at least one in pot galvanize metal base, hot-dip aluminizing zinc metal base and hot-dip aluminizing zinc magnesium metal base material, it is characterized in that, described coating is the cured product of metallic surface as above chromium treatment agent.
By technique scheme, at high temperature or after high temperature, have more excellent erosion resistance, and trivalent chromium in described coating at high temperature can not change sexavalent chrome into the coating that the present invention obtains through overcuring, meets environmental requirement completely.In addition, the storage endurance of metallic surface provided by the invention chromium treatment agent is very excellent, can at room temperature store 180 days and obvious proterties does not occur change and degradation after preparation completes.
Other features and advantages of the present invention are described in detail the embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
In the present invention, while not doing contrary explanation, the volume of gas and liquid is at 20 DEG C, the numerical value that standard atmosphere is depressed.In the present invention, in the situation that not doing contrary explanation, the particle dia that the scope of the term " solution " using is not limited to dispersate is less than the dispersed system (true solution) of 1nm, but makes a general reference the liquid form mixt of homogeneous, can comprise colloidal dispersion (colloidal solution).
On the one hand, the invention provides a kind of metallic surface chromium treatment agent, wherein, described metallic surface chromium treatment agent contains water, phosphonic acids complexing agent, poly carboxylic acid aqueous dispersant, aluminium dihydrogen phosphate, trivalent chromium source, cilicon oxide filler and water-soluble film-forming resin; Described phosphonic acids complexing agent is an alkali metal salt of Amino Trimethylene Phosphonic Acid and/or Amino Trimethylene Phosphonic Acid.
Wherein, in the chromium treatment agent of described metallic surface, the content of phosphonic acids complexing agent is 3-18g/L, is preferably 5-15g/L.
And in described trivalent chromium coating, with respect to the phosphonic acids complexing agent of every weight part, the content of poly carboxylic acid aqueous dispersant can be 0.5-2 weight part, is preferably 0.8-1.2 weight part.
In the chromium treatment agent of described metallic surface, with respect to the phosphonic acids complexing agent of every weight part, the content of aluminium dihydrogen phosphate can be 0.5-6 weight part, is preferably 1-3 weight part.
In the chromium treatment agent of described metallic surface, with respect to the phosphonic acids complexing agent of every weight part, with the cubage of chromium element, the content in trivalent chromium source can be 0.25-1.6 weight part, is preferably 0.5-1 weight part.
In the chromium treatment agent of described metallic surface, with respect to the phosphonic acids complexing agent of every weight part, the content of cilicon oxide filler can be 3-8 weight part, is preferably 4.5-6.5 weight part.
In the chromium treatment agent of described metallic surface, with respect to the phosphonic acids complexing agent of every weight part, the content of water-soluble film-forming resin can be 3-10 weight part; Be preferably 5.5-7.5 weight part.
For the performance of the coating that further the described metallic surface of raising chromium treatment agent forms, under preferable case, in the chromium treatment agent of described metallic surface, the content of phosphonic acids complexing agent is 5-15g/L, and, with respect to the phosphonic acids complexing agent of every weight part, the content of poly carboxylic acid aqueous dispersant is 0.8-1.2 weight part, the content of aluminium dihydrogen phosphate is 1-3 weight part, with the cubage of chromium element, the content in trivalent chromium source is 0.5-1 weight part, and the content of cilicon oxide filler is 4.5-6.5 weight part, and the content of water-soluble film-forming resin is 5.5-7.5 weight part.
Under preferable case, an alkali metal salt of described Amino Trimethylene Phosphonic Acid is at least one in Amino Trimethylene Phosphonic Acid four sodium, Amino Trimethylene Phosphonic Acid five sodium and Amino Trimethylene Phosphonic Acid potassium.
Wherein, described poly carboxylic acid aqueous dispersant can be for having the poly carboxylic acid material of ion chelating ability, for example poly aspartic acid or poly (sodium aspartate), under preferable case, described poly carboxylic acid aqueous dispersant is at least one in polyacrylic acid aqueous dispersant, sodium polyacrylate aqueous dispersant and hydrolytic polymaleic anhydride.Described polyacrylic acid aqueous dispersant can be for meeting the product of GB/T10533-2000; Described sodium polyacrylate aqueous dispersant can be for meeting the product of GB/T 2838-2010; Described hydrolytic polymaleic anhydride can be for meeting the product of GB/T 10535-1997; Described poly aspartic acid or poly (sodium aspartate) can be for meeting the product of HG/T3822-2006.The content of poly carboxylic acid aqueous dispersant and/or consumption calculate with solid.Herein solid with for calculating or representing that the solid implication of solid content is identical, be remaining composition after the desolventizing of poly carboxylic acid aqueous dispersant.
Wherein, described trivalent chromium source can be Cr (OH)
3, at least one in chromium sulphate, chromium nitrate, Plessy's green, biphosphate chromium, chromium trichloride, chromium acetate, chromic tartrate, chromium+oxalic acid, chromium citrate, chromium gluconate and toxilic acid chromium.
In the present invention, described cilicon oxide filler does not have special requirement, can be the various fillers taking silicon oxide as main body, and for example, 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, for example, the commercially available product that can to use purchased from the trade mark of Asahi Denka Co., Ltd. be AT-30, AT-30S, AT-40, AT-30A and AT-20, or be the commercially available product of SS-25 and SS-30 purchased from the trade mark of Shandong Bai Te novel material company limited.And, the content of cilicon oxide filler and/or consumption are to calculate with the weight of silicon oxide itself, the consumption of for example nano silicon dioxide sol is to calculate with the amount of the silicon-dioxide in colloidal sol, is multiplied by with the weight of nano silicon dioxide sol the numerical evaluation obtaining after its dioxide-containing silica percentage ratio (weight).
In the present invention, described water-soluble film-forming resin can be for various water miscible and can be used in modification or the unmodified resin of film forming, described resin can use with suitable goods form, for example water-soluble emulsion, at least one in water-soluble solution and water-soluble solid, the present invention does not have special requirement, as long as the film forming of can be used in, for example, described water-soluble film-forming resin can be the water-soluble polyester film-forming resin (water-soluble film-forming resin being obtained by polyalcohols monomer and polynary acids monomer polymerization, for example, purchased from Guangzhou Lapo Fine Chemicals Co., Ltd., the vibrin of trade mark CB2200), water-soluble phenylpropyl alcohol film-forming resin (by styrene monomer and vinylformic acid (ester) class monomer polymerization and water-soluble film-forming resin, for example, purchased from Guangzhou Chao Long Chemical Industry Science Co., Ltd, the trade mark is the benzene emulsion of xy-108b), soluble epoxide film-forming resin (the water-soluble film-forming resin being obtained by the monomer polymerization that contains epoxy group(ing), for example, purchased from Dongguan City Heima Chemical Co., Ltd., the trade mark is the epoxy resin of BH620), aqurous ployurethane film-forming resin (by multicomponent isocyanate class monomer and multi-hydroxy compounds monomer polymerization and water-soluble film-forming resin, for example, purchased from Jinjiang, Fujian Province Jian Hua company, the urethane resin of the trade mark 812), water-soluble silicon the third film-forming resin (by silicone based monomer and vinylformic acid (ester) class monomer polymerization and water-soluble film-forming resin, the for example Qingdao paint company TC-05 type organosilicon crylic acid latex of making the country prosperous, solid content is 48 % by weight), water-soluble acrylic film-forming resin (the water-soluble film-forming resin being obtained by vinylformic acid (ester) class monomer polymerization, the acrylic resin that is for example A-3418 purchased from the trade mark of Guangzhou Ou Peng chemical industry) and the water-soluble fluorine carbon film-forming resin (water-soluble film-forming resin being obtained by fluorinated monomer polymerization, for example, purchased from Beijing Shouchuang Nano Techn Co., Ltd., the trade mark is the water-base fluorocarbon emulsion of SKFT-I) at least one, under preferable case, described water-soluble film-forming resin is at least one in water-soluble phenylpropyl alcohol film-forming resin, soluble epoxide film-forming resin, water-soluble silicon the third film-forming resin, water-soluble acrylic film-forming resin, aqurous ployurethane film-forming resin and water-soluble polyester film-forming resin.More preferably, described water-soluble film-forming resin is water-soluble 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 with for calculating or representing that the solid implication of solid content is identical, be water-soluble film-forming resin except remaining composition after desolventizing.
Wherein, under preferable case, described metallic surface chromium treatment agent also contains sodium phosphate, and with respect to the phosphonic acids complexing agent of every weight part, the content of sodium phosphate is 0.5-4 weight part, more preferably 1-2 weight part; And described trivalent chromium source obtains by reductive agent reduction of hexavalent chromium compound.Particularly, the method in can reference literature CN101608073B is prepared trivalent chromium source.
On the other hand, the present invention also provides a kind of method of preparing metallic surface chromium treatment agent, and wherein, the method comprises: (1) prepares the first solution, and described the first solution contains phosphonic acids complexing agent, poly carboxylic acid aqueous dispersant and aluminium dihydrogen phosphate; Described phosphonic acids complexing agent is an alkali metal salt of Amino Trimethylene Phosphonic Acid and/or Amino Trimethylene Phosphonic Acid; (2) prepare the second solution, described the second solution contains trivalent chromium source, nano silicon, water-soluble film-forming resin; (3) described the first solution and the second solution are mixed.
Wherein, in the method, with respect to the phosphonic acids complexing agent of every weight part, the consumption of poly carboxylic acid aqueous dispersant can be 0.5-2 weight part, is preferably 0.8-1.2 weight part.
Wherein, in the method, with respect to the phosphonic acids complexing agent of every weight part, the consumption of aluminium dihydrogen phosphate can be 0.5-6 weight part, is preferably 1-3 weight part.
Wherein, in the method, with respect to the phosphonic acids complexing agent of every weight part, with the cubage of chromium element, the consumption in trivalent chromium source can be 0.25-1.6 weight part, is preferably 0.5-1 weight part.
Wherein, in the method, with respect to the phosphonic acids complexing agent of every weight part, the consumption of cilicon oxide filler can be 3-8 weight part, is preferably 4.5-6.5 weight part.
Wherein, in the method, with respect to the phosphonic acids complexing agent of every weight part, the consumption of water-soluble film-forming resin can be 3-10 weight part; Be preferably 5.5-7.5 weight part.
Wherein, in the method, can be 3-18g/L by regulating the add-on of water to make the consumption of the phosphonic acids complexing agent in the chromium treatment agent of metallic surface; Be preferably 5-15g/L.Can be chosen in the add-on that at least one in the mixture of the first solution, the second solution and the first solution and the second solution regulates water.
Under preferable case, in the first solution, the content of phosphonic acids complexing agent is 10-30 % by weight.Under preferable case, in the second solution, the content in trivalent chromium source is 0.07-3 % by weight.
For the performance of the coating that further the described metallic surface of raising chromium treatment agent forms, under preferable case, with respect to the phosphonic acids complexing agent of every weight part, the consumption of poly carboxylic acid aqueous dispersant is 0.8-1.2 weight part, the consumption of aluminium dihydrogen phosphate is 1-3 weight part, with the cubage of chromium element, the consumption in trivalent chromium source is 0.5-1 weight part, the consumption of cilicon oxide filler is 4.5-6.5 weight part, the consumption of water-soluble film-forming resin is 5.5-7.5 weight part, and, be 5-15g/L by regulating the add-on of water to make the content of the phosphonic acids complexing agent in the chromium treatment agent of metallic surface.
Under preferable case, at least one in described Amino Trimethylene Phosphonic Acid four sodium, Amino Trimethylene Phosphonic Acid five sodium and Amino Trimethylene Phosphonic Acid potassium.Wherein, described poly carboxylic acid aqueous dispersant can be for having the poly carboxylic acid material of ion chelating ability, for example poly aspartic acid or poly (sodium aspartate), under preferable case, described poly carboxylic acid aqueous dispersant is at least one in polyacrylic acid aqueous dispersant, sodium polyacrylate aqueous dispersant and hydrolytic polymaleic anhydride.Described polyacrylic acid aqueous dispersant can be for meeting the product of GB/T10533-2000; Described sodium polyacrylate aqueous dispersant can be for meeting the product of GB/T 2838-2010; Described hydrolytic polymaleic anhydride can be for meeting the product of GB/T 10535-1997; Described poly aspartic acid or poly (sodium aspartate) can be for meeting the product of HG/T3822-2006.The content of poly carboxylic acid aqueous dispersant and/or consumption calculate with solid.Herein solid with for calculating or representing that the solid implication of solid content is identical, be remaining composition after the desolventizing of poly carboxylic acid aqueous dispersant.
Wherein, described trivalent chromium source can be Cr (OH)
3, at least one in chromium sulphate, chromium nitrate, Plessy's green, biphosphate chromium, chromium trichloride, chromium acetate, chromic tartrate, chromium+oxalic acid, chromium citrate, chromium gluconate and toxilic acid chromium.
In the present invention, described cilicon oxide filler does not have special requirement, can be the various fillers taking silicon oxide as main body, and for example, 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, for example, the commercially available product that can to use purchased from the trade mark of Asahi Denka Co., Ltd. be AT-30, AT-30S, AT-40, AT-30A and AT-20, or be the commercially available product of SS-25 and SS-30 purchased from the trade mark of Shandong Bai Te novel material company limited.And, the content of cilicon oxide filler and/or consumption are to calculate with the weight of silicon oxide itself, the consumption of for example nano silicon dioxide sol is to calculate with the amount of the silicon-dioxide in colloidal sol, is multiplied by with the weight of nano silicon dioxide sol the numerical evaluation obtaining after its dioxide-containing silica percentage ratio (weight).
In the present invention, described water-soluble film-forming resin can be for various water miscible and can be used in modification or the unmodified resin of film forming, described resin can use with suitable goods form, for example water-soluble emulsion, at least one in water-soluble solution and water-soluble solid, the present invention does not have special requirement, as long as the film forming of can be used in, for example, described water-soluble film-forming resin can be the water-soluble polyester film-forming resin (water-soluble film-forming resin being obtained by polyalcohols monomer and polynary acids monomer polymerization, for example, purchased from Guangzhou Lapo Fine Chemicals Co., Ltd., the vibrin of trade mark CB2200), water-soluble phenylpropyl alcohol film-forming resin (by styrene monomer and vinylformic acid (ester) class monomer polymerization and water-soluble film-forming resin, for example, purchased from Guangzhou Chao Long Chemical Industry Science Co., Ltd, the trade mark is the benzene emulsion of xy-108b), soluble epoxide film-forming resin (the water-soluble film-forming resin being obtained by the monomer polymerization that contains epoxy group(ing), for example, purchased from Dongguan City Heima Chemical Co., Ltd., the trade mark is the epoxy resin of BH620), aqurous ployurethane film-forming resin (by multicomponent isocyanate class monomer and multi-hydroxy compounds monomer polymerization and water-soluble film-forming resin, for example, purchased from Jinjiang, Fujian Province Jian Hua company, the urethane resin of the trade mark 812), water-soluble silicon the third film-forming resin (by silicone based monomer and vinylformic acid (ester) class monomer polymerization and water-soluble film-forming resin, the for example Qingdao paint company TC-05 type organosilicon crylic acid latex of making the country prosperous, solid content is 48 % by weight), water-soluble acrylic film-forming resin (the water-soluble film-forming resin being obtained by vinylformic acid (ester) class monomer polymerization, the acrylic resin that is for example A-3418 purchased from the trade mark of Guangzhou Ou Peng chemical industry) and the water-soluble fluorine carbon film-forming resin (water-soluble film-forming resin being obtained by fluorinated monomer polymerization, for example, purchased from Beijing Shouchuang Nano Techn Co., Ltd., the trade mark is the water-base fluorocarbon emulsion of SKFT-I) at least one, under preferable case, described water-soluble film-forming resin is at least one in water-soluble phenylpropyl alcohol film-forming resin, soluble epoxide film-forming resin, water-soluble silicon the third film-forming resin, water-soluble acrylic film-forming resin, aqurous ployurethane film-forming resin and water-soluble polyester film-forming resin.More preferably, described water-soluble film-forming resin is water-soluble 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 with for calculating or representing that the solid implication of solid content is identical, be water-soluble film-forming resin except remaining composition after desolventizing.
Wherein, under preferable case, described the second solution also has sodium phosphate, and with respect to the phosphonic acids complexing agent of every weight part, the consumption of sodium phosphate is 0.5-4 weight part, is preferably 1-2 weight part; And described trivalent chromium source obtains by reductive agent reduction of hexavalent chromium compound.Particularly, the method in can reference literature CN101608073B is prepared trivalent chromium source.While obtaining trivalent chromium source by reductive agent reduction of hexavalent chromium compound, the amount in trivalent chromium source is calculated with hexavalent chromium compound.
On the other hand, the present invention also provides the metallic surface preparing according to aforesaid method chromium treatment agent.
On the other hand, the present invention also provides a kind of hot-dip metal plated material, this hot-dip metal plated material comprises hot-dip metal plated base material and is attached to the coating on this hot-dip metal plated base material, described hot-dip metal plated base material is at least one in pot galvanize metal base, hot-dip aluminizing zinc metal base and hot-dip aluminizing zinc magnesium metal base material, it is characterized in that, described coating is the cured product of metallic surface as above chromium treatment agent.
Wherein, the thickness of described coating can be the known thickness of passive film on zinc-plating material, and the present invention has no particular limits, and overweight coating tack declines, and cover light solidity to corrosion declines, and therefore, under preferable case, the thickness of described coating is 0.1-1 micron.
Wherein, the method for adhering to described coating on zinc-plated base material comprises described surface treatment agent is attached on zinc-plated base material, and then dry, dry temperature can be 60-120 DEG C, and the time can be 0.5-3 second.
In order to make the thickness of described coating meet above-mentioned requirement, the usage quantity of described surface treatment agent on the zinc-plated base material of unit surface can correspondingly be adjusted, for example, in the time requiring the thickness of described coating to be 0.5-1.5 micron, the zinc-plated substrate surface of every square metre relatively, the consumption of described surface treatment agent can be 0.2-1.5g.
In the present invention, the volume of all liquid and gas all refers to 20 DEG C, the volume that 1 standard atmosphere is depressed.
In the present invention, the solid content of various organic binders and viscosity and the method specifying according to standard GB/T/T 2793 and GB/T1723 are respectively measured and record.
Below will describe the present invention by embodiment, but scope of the present invention is not limited in embodiment.
Preparation Example 1
This Preparation Example is for illustrating that the method for reference literature CN101608073B obtains trivalent chromium source by reductive agent reduction of hexavalent chromium compound.
In the enamel reaction still of 3000 liters, add 300 kilograms of deionized waters, then add 50 kilograms of chromic trioxide (CrO
3), the agitator that starts reactor stirs 10 minutes, and chromic trioxide is dissolved.After chromic trioxide dissolves completely, at room temperature add the citric acid of double centner, start rapidly agitator, citric acid is dissolved fast.In the time that solution does not emit bubble, judge and reacted, obtain required trivalent chromium source.
Embodiment 1
By the phosphonic acids complexing agent (Amino Trimethylene Phosphonic Acid of 10g, purchased from Shandong Taihe Water Treatment Co., Ltd., numbering CAS No.6419-19-8), the poly carboxylic acid aqueous dispersant (polyacrylic acid of 10g, purchased from Shandong Taihe Water Treatment Co., Ltd., numbering CAS No.9003-01-4) and the aluminium dihydrogen phosphate of 20g add in 20g water, under the stirring velocity of 1500 revs/min, be mixed to evenly, obtain the first solution.
By (the trivalent chromium source that Preparation Example 1 prepares, the trivalent chromium source of 7g, add-on is calculated with the amount of chromium element), cilicon oxide filler (the nano silicon dioxide sol of 56g, purchased from Shandong Bai Te novel material company limited, the trade mark is SS-30, add-on is in silicon-dioxide), the water-soluble film-forming resin of 65g is (by the benzene emulsion of equivalent (purchased from Guangzhou Chao Long Chemical Industry Science Co., Ltd, the trade mark is xy-108b benzene emulsion, solid content is 48 % by weight, viscosity is 500-1000mPas) and fluorine carbon emulsion (purchased from Beijing Shouchuang Nano Techn Co., Ltd., the trade mark is the water-base fluorocarbon emulsion of SKFT-I, solid content is 45 % by weight, viscosity is 500-1000mPas) composition) and 15g sodium phosphate add in 585g water, under the stirring velocity of 1500 revs/min, be mixed to evenly, obtain the second solution.
Merge the first solution and the second solution, and water to adjust volume be 1L, under the stirring velocity of 1500 revs/min, be mixed to evenly, obtain uniform liquid.This uniform liquid is the metallic surface chromium treatment agent of the present embodiment.
Embodiment 2
By the phosphonic acids complexing agent of 10g (Amino Trimethylene Phosphonic Acid five sodium, purchased from Shandong Taihe Water Treatment Co., Ltd., numbering CAS No.2235-43-0), the poly carboxylic acid aqueous dispersant (sodium polyacrylate of 12g, purchased from Shandong Taihe Water Treatment Co., Ltd., numbering CAS No.9003-04-7) and the aluminium dihydrogen phosphate of 10g add in 30g water, under the stirring velocity of 1500 revs/min, be mixed to evenly, obtain the first solution.
By (the trivalent chromium source that Preparation Example 1 prepares, the trivalent chromium source of 5g, add-on is calculated with the amount of chromium element), cilicon oxide filler (the nano silicon dioxide sol of 65g, purchased from Shandong Bai Te novel material company limited, the trade mark is SS-30, add-on 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 % by weight, viscosity is 500-1000mPas)) and 10g sodium phosphate add in 570g water, under the stirring velocity of 1500 revs/min, be mixed to evenly, obtain the second solution.
Merge the first solution and the second solution, and water to adjust volume be 1L, under the stirring velocity of 1500 revs/min, be mixed to evenly, obtain uniform liquid.This uniform liquid is the metallic surface chromium treatment agent of the present embodiment.
Embodiment 3
By the phosphonic acids complexing agent of 10g (Amino Trimethylene Phosphonic Acid four sodium, purchased from Shandong Taihe Water Treatment Co., Ltd., be numbered CAS No.20592-85-2), the poly carboxylic acid aqueous dispersant (hydrolytic polymaleic anhydride of 8g, purchased from Shandong Taihe Water Treatment Co., Ltd., numbering CAS No.26099-09-02) and the aluminium dihydrogen phosphate of 30g add in 30g water, under the stirring velocity of 1500 revs/min, be mixed to evenly, obtain the first solution.
By (the trivalent chromium source that Preparation Example 1 prepares, the trivalent chromium source of 10g, add-on is calculated with the amount of chromium element), cilicon oxide filler (the nano silicon dioxide sol of 45g, purchased from Shandong Bai Te novel material company limited, the trade mark is SS-30, add-on is in silicon-dioxide), (benzene 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 benzene emulsion, solid content is 48 % by weight, viscosity is 500-1000mPas)) and 20g sodium phosphate add in 595g water, under the stirring velocity of 1500 revs/min, be mixed to evenly, obtain the second solution.
Merge the first solution and the second solution, and water to adjust volume be 1L, under the stirring velocity of 1500 revs/min, be mixed to evenly, obtain uniform liquid.This uniform liquid is the metallic surface chromium treatment agent of the present embodiment.
Embodiment 4
By the phosphonic acids complexing agent (Amino Trimethylene Phosphonic Acid of 10g, purchased from Shandong Taihe Water Treatment Co., Ltd., numbering CAS No.6419-19-8), the poly carboxylic acid aqueous dispersant (polyacrylic acid of 10g, purchased from Shandong Taihe Water Treatment Co., Ltd., numbering CAS No.9003-01-4) and the aluminium dihydrogen phosphate of 20g add in 20g water, under the stirring velocity of 1500 revs/min, be mixed to evenly, obtain the first solution.
By trivalent chromium source (the biphosphate chromium of 7g, add-on is calculated with the amount of chromium element), cilicon oxide filler (the nano silicon dioxide sol of 56g, purchased from Shandong Bai Te novel material company limited, the trade mark is SS-30, add-on is in silicon-dioxide), the water-soluble film-forming resin of 65g is (by the benzene emulsion of equivalent (purchased from Guangzhou Chao Long Chemical Industry Science Co., Ltd, the trade mark is xy-108b benzene emulsion, solid content is 48 % by weight, viscosity is 500-1000mPas) and fluorine carbon emulsion (purchased from Beijing Shouchuang Nano Techn Co., Ltd., the trade mark is the water-base fluorocarbon emulsion of SKFT-I, solid content is 45 % by weight, viscosity is 500-1000mPas) composition) add in 590g water, under the stirring velocity of 1500 revs/min, be mixed to evenly, obtain the second solution.
Merge the first solution and the second solution, and water to adjust volume be 1L, under the stirring velocity of 1500 revs/min, be mixed to evenly, obtain uniform liquid.This uniform liquid is the metallic surface chromium treatment agent of the present embodiment.
Embodiment 5
By the phosphonic acids complexing agent (Amino Trimethylene Phosphonic Acid of 10g, purchased from Shandong Taihe Water Treatment Co., Ltd., numbering CAS No.6419-19-8), the poly carboxylic acid aqueous dispersant (polyacrylic acid of 5g, purchased from Shandong Taihe Water Treatment Co., Ltd., numbering CAS No.9003-01-4) and the aluminium dihydrogen phosphate of 60g add in 60g water, under the stirring velocity of 1500 revs/min, be mixed to evenly, obtain the first solution.
By (the trivalent chromium source that Preparation Example 1 prepares, the trivalent chromium source of 16g, add-on is calculated with the amount of chromium element), cilicon oxide filler (the nano silicon dioxide sol of 30g, purchased from Shandong Bai Te novel material company limited, the trade mark is SS-30, add-on is in silicon-dioxide), the water-soluble film-forming resin of 30g is (by the benzene emulsion of equivalent (purchased from Guangzhou Chao Long Chemical Industry Science Co., Ltd, the trade mark is xy-108b benzene emulsion, solid content is 48 % by weight, viscosity is 500-1000mPas) and fluorine carbon emulsion (purchased from Beijing Shouchuang Nano Techn Co., Ltd., the trade mark is the water-base fluorocarbon emulsion of SKFT-I, solid content is 45 % by weight, viscosity is 500-1000mPas) composition) and 15g sodium phosphate add in 560g water, under the stirring velocity of 1500 revs/min, be mixed to evenly, obtain the second solution.
Merge the first solution and the second solution, and water to adjust volume be 1L, under the stirring velocity of 1500 revs/min, be mixed to evenly, obtain uniform liquid.This uniform liquid is the metallic surface chromium treatment agent of the present embodiment.
Embodiment 6
By the phosphonic acids complexing agent (Amino Trimethylene Phosphonic Acid of 10g, purchased from Shandong Taihe Water Treatment Co., Ltd., numbering CAS No.6419-19-8), the poly carboxylic acid aqueous dispersant (polyacrylic acid of 20g, purchased from Shandong Taihe Water Treatment Co., Ltd., numbering CAS No.9003-01-4) and the aluminium dihydrogen phosphate of 5g add in 20g water, under the stirring velocity of 1500 revs/min, be mixed to evenly, obtain the first solution.
By (the trivalent chromium source that Preparation Example 1 prepares, the trivalent chromium source of 2.5g, add-on is calculated with the amount of chromium element), cilicon oxide filler (the nano silicon dioxide sol of 80g, purchased from Shandong Bai Te novel material company limited, the trade mark is SS-30, add-on is in silicon-dioxide), the water-soluble film-forming resin of 100g is (by the benzene emulsion of equivalent (purchased from Guangzhou Chao Long Chemical Industry Science Co., Ltd, the trade mark is xy-108b benzene emulsion, solid content is 48 % by weight, viscosity is 500-1000mPas) and fluorine carbon emulsion (purchased from Beijing Shouchuang Nano Techn Co., Ltd., the trade mark is the water-base fluorocarbon emulsion of SKFT-I, solid content is 45 % by weight, viscosity is 500-1000mPas) composition) and 15g sodium phosphate add in 545g water, under the stirring velocity of 1500 revs/min, be mixed to evenly, obtain the second solution.
Merge the first solution and the second solution, and water to adjust volume be 1L, under the stirring velocity of 1500 revs/min, be mixed to evenly, obtain uniform liquid.This uniform liquid is the metallic surface chromium treatment agent of the present embodiment.
Embodiment 7
Prepare chromium ion passivating solution according to the method for embodiment 1, different, use poly aspartic acid (PASP, purchased from Shandong Taihe Water Treatment Co., Ltd., numbers CAS No.181828-06-8) as poly carboxylic acid aqueous dispersant.
Comparative example 1
Prepare metallic surface chromium treatment agent according to the method for embodiment 1, different, use PAPE (PAPE, purchased from Shandong Taihe Water Treatment Co., Ltd.) as phosphonic acids complexing agent.
Comparative example 2
Prepare metallic surface chromium treatment agent according to the method for embodiment 1, different, phosphonic acids complexing agent is replaced with to phytic acid.
Preparation Example 2
Get the metallic surface chromium treatment agent that embodiment 1-7 and comparative example 1 obtain and be coated on respectively steel plate galvanized (purchased from Pangang Group Panzhihua Steel Vanadium Co., Ltd., model DX54D, in zinc coating containing zinc 95 % by weight) surface, warm air drying 2 seconds, obtains respectively steel plate galvanized after treatment at 90-110 DEG C.Wherein, coating amount makes the thickness of the coating on steel plate galvanized after treatment be 0.8 micron.The thickness of coating is to use XRF(fluorescence spectrophotometer) survey meter measure numerical value.Wherein, the metallic surface chromium treatment agent using in this Preparation Example is all to have stored the metallic surface chromium treatment agent of 1 day after having prepared (obtaining uniform liquid).
Preparation Example 3-5
Prepare steel plate galvanized after treatment according to the method for Preparation Example 2, different, the metallic surface chromium treatment agent of use is all to have stored the metallic surface chromium treatment agent of 60,120 and 180 days after having prepared (obtaining uniform liquid).
Test implementation example 1
By the requirement specifying in GB/T101251997, carry out neutral salt spray test, measure respectively the steel plate galvanized after treatment of Preparation Example 2-5 400 DEG C of corrosion resisting properties of toasting after 30s.It is qualified to be considered as by " salt-fog test 168h, corrosion area < 3% ".
Test result as above is as shown in table 1.Number of days in bracket represents the storage time of metallic surface chromium treatment agent.
According to GB 21275-2007 " limiting the use of material sexavalent chrome detection method in electronic and electrical equipment " specified standards test content of 6-valence Cr ions, the results are shown in table 1(and only list), it is qualified that content of 6-valence Cr ions is considered as lower than 2ppm.
Table 1
Can find out from the data of table 1, the solidity to corrosion of the protective film that metallic surface provided by the invention chromium treatment agent forms is very good, and the storage endurance of metallic surface provided by the invention chromium treatment agent is also very good.And, visible according to the data of table 1, content at preferred phosphonic acids complexing agent is 5-15g/L, and, with respect to the phosphonic acids complexing agent of every weight part, the content of poly carboxylic acid aqueous dispersant is 0.8-1.2 weight part, the content of aluminium dihydrogen phosphate is 1-3 weight part, with the cubage of chromium element, the content in trivalent chromium source is 0.5-1 weight part, the content of cilicon oxide filler is 4.5-6.5 weight part, and the content of water-soluble film-forming resin is in the situation of 5.5-7.5 weight part, can further improve the solidity to corrosion of the protective film of described metallic surface chromium treatment agent formation.And, visible according to the data of table 1, be at least one in polyacrylic acid aqueous dispersant, sodium polyacrylate aqueous dispersant and hydrolytic polymaleic anhydride at preferred described poly carboxylic acid aqueous dispersant, can further improve the solidity to corrosion of the protective film of described trivalent chromium coating formation.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characterictic described in above-mentioned embodiment, in reconcilable situation, can combine by any suitable mode, for fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible array modes.
In addition, also can carry out arbitrary combination between various embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. a metallic surface chromium treatment agent, described metallic surface chromium treatment agent contains water, phosphonic acids complexing agent, poly carboxylic acid aqueous dispersant, aluminium dihydrogen phosphate, trivalent chromium source, cilicon oxide filler and water-soluble film-forming resin, and described phosphonic acids complexing agent is an alkali metal salt of Amino Trimethylene Phosphonic Acid and/or Amino Trimethylene Phosphonic Acid.
2. metallic surface according to claim 1 chromium treatment agent, wherein, the content of phosphonic acids complexing agent is 3-18g/L, and, with respect to the phosphonic acids complexing agent of every weight part, the content of poly carboxylic acid aqueous dispersant is 0.5-2 weight part, the content of aluminium dihydrogen phosphate is 0.5-6 weight part, and with the cubage of chromium element, the content in trivalent chromium source is 0.25-1.6 weight part, the content of cilicon oxide filler is 3-8 weight part, and the content of water-soluble film-forming resin is 3-10 weight part;
Preferably, the content of phosphonic acids complexing agent is 5-15g/L, and, with respect to the phosphonic acids complexing agent of every weight part, the content of poly carboxylic acid aqueous dispersant is 0.8-1.2 weight part, and the content of aluminium dihydrogen phosphate is 1-3 weight part, with the cubage of chromium element, the content in trivalent chromium source is 0.5-1 weight part, and the content of cilicon oxide filler is 4.5-6.5 weight part, and the content of water-soluble film-forming resin is 5.5-7.5 weight part.
3. metallic surface according to claim 1 and 2 chromium treatment agent, wherein,
An alkali metal salt of described Amino Trimethylene Phosphonic Acid is at least one in Amino Trimethylene Phosphonic Acid four sodium, Amino Trimethylene Phosphonic Acid five sodium and Amino Trimethylene Phosphonic Acid potassium;
Described poly carboxylic acid aqueous dispersant is at least one in polyacrylic acid aqueous dispersant, sodium polyacrylate aqueous dispersant and hydrolytic polymaleic anhydride;
Described trivalent chromium source is Cr (OH)
3, at least one in chromium sulphate, chromium nitrate, Plessy's green, biphosphate chromium, chromium trichloride, chromium acetate, chromic tartrate, chromium+oxalic acid, chromium citrate, chromium gluconate and toxilic 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-soluble phenylpropyl alcohol film-forming resin, soluble epoxide film-forming resin, aqurous ployurethane film-forming resin, water-soluble silicon the third film-forming resin, water-soluble acrylic film-forming resin and water-soluble fluorine carbon film-forming resin.
4. metallic surface according to claim 1 and 2 chromium treatment agent, wherein, described metallic surface chromium treatment agent also contains sodium phosphate, and with respect to the phosphonic acids complexing agent of every weight part, the content of sodium phosphate is 0.5-4 weight part, is preferably 1-2 weight part;
And described trivalent chromium source obtains by reductive agent reduction of hexavalent chromium compound.
5. a method of preparing metallic surface chromium treatment agent, is characterized in that, the method comprises:
(1) prepare the first solution, described the first solution contains phosphonic acids complexing agent, poly carboxylic acid aqueous dispersant and aluminium dihydrogen phosphate; Described phosphonic acids complexing agent is an alkali metal salt of Amino Trimethylene Phosphonic Acid and/or Amino Trimethylene Phosphonic Acid;
(2) prepare the second solution, described the second solution contains trivalent chromium source, nano silicon, water-soluble film-forming resin;
(3) described the first solution and the second solution are mixed.
6. method according to claim 5, wherein, with respect to the phosphonic acids complexing agent of every weight part, the consumption of poly carboxylic acid aqueous dispersant is 0.5-2 weight part, the consumption of aluminium dihydrogen phosphate is 0.5-6 weight part, with the cubage of chromium element, the consumption in trivalent chromium source is 0.25-1.6 weight part, the consumption of cilicon oxide filler is 3-8 weight part, the consumption of water-soluble film-forming resin is 3-10 weight part, and, be 3-18g/L by regulating the add-on of water to make the content of the phosphonic acids complexing agent in the chromium treatment agent of metallic surface;
Preferably, with respect to the phosphonic acids complexing agent of every weight part, the consumption of poly carboxylic acid aqueous dispersant is 0.8-1.2 weight part, the consumption of aluminium dihydrogen phosphate is 1-3 weight part, and with the cubage of chromium element, the consumption in trivalent chromium source is 0.5-1 weight part, the consumption of cilicon oxide filler is 4.5-6.5 weight part, the consumption of water-soluble film-forming resin is 5.5-7.5 weight part, and, be 5-15g/L by regulating the add-on of water to make the content of the phosphonic acids complexing agent in the chromium treatment agent of metallic surface.
7. according to the method described in claim 5 or 6, wherein,
An alkali metal salt of described Amino Trimethylene Phosphonic Acid is at least one in Amino Trimethylene Phosphonic Acid four sodium, Amino Trimethylene Phosphonic Acid five sodium and Amino Trimethylene Phosphonic Acid potassium;
Described poly carboxylic acid aqueous dispersant is at least one in polyacrylic acid aqueous dispersant, sodium polyacrylate aqueous dispersant and hydrolytic polymaleic anhydride;
Described trivalent chromium source is Cr (OH)
3, at least one in chromium sulphate, chromium nitrate, Plessy's green, biphosphate chromium, chromium trichloride, chromium acetate, chromic tartrate, chromium+oxalic acid, chromium citrate, chromium gluconate and toxilic 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-soluble phenylpropyl alcohol film-forming resin, soluble epoxide film-forming resin, aqurous ployurethane film-forming resin, water-soluble silicon the third film-forming resin, water-soluble acrylic film-forming resin and water-soluble fluorine carbon film-forming resin.
8. according to the method described in claim 5 or 6, wherein, described the second solution also has sodium phosphate, and with respect to the phosphonic acids complexing agent of every weight part, the consumption of sodium phosphate is 0.5-4 weight part, is preferably 1-2 weight part;
And described trivalent chromium source obtains by reductive agent reduction of hexavalent chromium compound.
9. the metallic surface chromium treatment agent that in claim 5-8, described in any one, method prepares.
10. a hot-dip metal plated material, this hot-dip metal plated material comprises hot-dip metal plated base material and is attached to the coating on this hot-dip metal plated base material, described hot-dip metal plated base material is at least one in pot galvanize metal base, hot-dip aluminizing zinc metal base and hot-dip aluminizing zinc magnesium metal base material, it is characterized in that, described coating is the cured product of the metallic surface chromium treatment agent described in any one in claim 1-4 and 9.
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| CN111356786A (en) * | 2017-10-30 | 2020-06-30 | 巴克化学制品公司 | Method and composition for treating metal surfaces with trivalent chromium compounds |
| CN111441043A (en) * | 2020-06-02 | 2020-07-24 | 广东比格莱科技有限公司 | Zinc-plated trivalent chromium color passivator and preparation method thereof |
| CN115583710A (en) * | 2022-07-19 | 2023-01-10 | 江苏驰佳环保科技有限公司 | Chelating agent and preparation method thereof |
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