CN104073074B - A kind of metal surface chromium inorganic agent and preparation method thereof and hot-dip metal plated material - Google Patents
A kind of metal surface chromium inorganic agent and preparation method thereof and hot-dip metal plated material Download PDFInfo
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- CN104073074B CN104073074B CN201310400141.8A CN201310400141A CN104073074B CN 104073074 B CN104073074 B CN 104073074B CN 201310400141 A CN201310400141 A CN 201310400141A CN 104073074 B CN104073074 B CN 104073074B
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Abstract
The invention provides a kind of metal surface chromium inorganic agent, wherein, described metal surface chromium inorganic agent contains water, phosphonic acids complexing agent, polycarboxylic acids aqueous dispersion, aluminium dihydrogen phosphate, trivalent chromium source, cilicon oxide filler and water-soluble film-forming resin；Described phosphonic acids complexing agent is the alkali metal salt of ATMP and/or ATMP.Present invention also offers a kind of method preparing metal surface chromium inorganic agent.Present invention also offers the metal surface chromium inorganic agent 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, and described coating is the cured product of metal surface as above chromium inorganic agent.The present invention at high temperature or has the trivalent chromium in more excellent corrosion resistance, and described coating through the coating that overcuring obtains after high temperature 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 metal surface chromium inorganic agent, one
The method of preparation metal surface chromium inorganic agent, the method the metal surface chromium inorganic agent obtained and one heat
Metallization.
Background technology
Hot-dip metal plated material, including hot-dip galvanized metal material and hot-dip aluminizing zinc metal material, in order to prevent sending out
Get rusty erosion, all can be at the surface of hot-dip metal plated material coating layer of metal protective coating to form protecting film.
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,
There is bigger occupation rate of market.But, parliament of European Union and council passed through on February 13rd, 2003
" the Restriction of the Use of Certain Hazardous Substances in Electrical and Electronic Equipment ", is called for short RoHS instruction, i.e. Europe
Alliance the 2002/95/ECth instruction.This command request was newly put on market after on July 1st, 2006
In electronic and electrical equipment, the material being prevented or restricted from using has lead (Pb), mercury (Hg), cadmium (Cd), sexavalence
Chromium (Cr6+).Wherein, lead (Pb), Cr VI (Cr6+), cadmium (Cd), mercury (Hg) belong to limit steel plate composition or
Coating composition or coating composition.
Therefore, at home and abroad in market, the use of chromyl coating is greatly limited, mesh
Before, the developing focus of metal protection coating transfers to the most chromyl environment-friendly type coating, particularly trivalent
Chromium ion coating.
Such as, CN102477551A discloses a kind of surface conditioning agent, falls within a kind of trivalent chromic ion
Coating, this trivalent chromic ion coating contains styrene-acrylic emulsion and/or silicone acrylic emulsion, fluorine carbon emulsion and/or fluorine silicon
Emulsion, trivalent chromium compound and phosphate.
But it is demonstrated experimentally that the corrosion resistance of the protecting film of this trivalent chromic ion coating formation is the most relatively low.
Summary of the invention
In order to the corrosion resistance overcoming the protecting film of existing metal surface chromium inorganic agent formation is the most relatively low
Defect, the invention provides a kind of metal surface chromium inorganic agent, a kind of metal surface chromium inorganic agent of preparing
Method, the method the metal surface chromium inorganic agent obtained and the hot-dip metal plated material of one.
On the one hand, the invention provides a kind of metal surface chromium inorganic agent, wherein, described metal surface chromium
Inorganic agent contain water, phosphonic acids complexing agent, polycarboxylic acids aqueous dispersion, aluminium dihydrogen phosphate, trivalent chromium source,
Cilicon oxide filler and water-soluble film-forming resin；Described phosphonic acids complexing agent is ATMP and/or amino
The alkali metal salt of three methylenephosphonic acids.
On the other hand, present invention also offers a kind of method preparing metal surface chromium inorganic agent, wherein,
The method includes: (1) prepares the first solution, and described first solution contains phosphonic acids complexing agent, polycarboxylic acids water
Property dispersant and aluminium dihydrogen phosphate；Described phosphonic acids complexing agent is ATMP and/or amino three methene
The alkali metal salt of phosphonic acids；(2) preparing the second solution, described second solution contains trivalent chromium source, nanometer two
Silica, water-soluble film-forming resin；(3) described first solution and the second solution are mixed.
On the other hand, present invention also offers the metal surface chromium prepared according to said method to process
Agent.
On the other hand, present invention also offers a kind of hot-dip metal plated material, this hot-dip metal plated material includes heat
Plating base material and the coating being attached on this hot-dip metal plated base material, described hot-dip metal plated base material is galvanizing
At least one in metal base, hot-dip aluminizing zinc metal base and hot-dip aluminizing zinc magnesium metal base material, its feature
Being, described coating is the cured product of metal surface as above chromium inorganic agent.
By technique scheme, the coating that the present invention obtains through overcuring at high temperature or has after high temperature
Trivalent chromium in more excellent corrosion resistance, and described coating at high temperature will not be changed into sexavalence
Chromium, complies fully with environmental requirement.Additionally, the storage endurance of the metal surface chromium inorganic agent of present invention offer
The most excellent, can at room temperature store 180 days after preparation completes and do not occur obvious proterties change and
Hydraulic performance decline.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that this place is retouched
The detailed description of the invention stated is merely to illustrate and explains the present invention, 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, a standard
Numerical value under atmospheric pressure.In the present invention, in the case of illustrating on the contrary, the term of use is " molten
Liquid " scope be not limited to the particle diameter of the dispersate disperse system (true solution) less than 1nm, but general
Refer to homogeneous liquefied mixture, colloidal dispersion (colloidal solution) can be included.
On the one hand, the invention provides a kind of metal surface chromium inorganic agent, wherein, described metal surface chromium
Inorganic agent contain water, phosphonic acids complexing agent, polycarboxylic acids aqueous dispersion, aluminium dihydrogen phosphate, trivalent chromium source,
Cilicon oxide filler and water-soluble film-forming resin；Described phosphonic acids complexing agent is ATMP and/or amino
The alkali metal salt of three methylenephosphonic acids.
Wherein, in the chromium inorganic agent of described metal surface, the content of phosphonic acids complexing agent is 3-18g/L, preferably
For 5-15g/L.
Further, in described chromium, relative to the phosphonic acids complexing agent of every weight portion, polycarboxylic acids is aqueous
The content of dispersant can be 0.5-2 weight portion, preferably 0.8-1.2 weight portion.
In the chromium inorganic agent of described metal surface, relative to the phosphonic acids complexing agent of every weight portion, aluminium dihydrogen phosphate
Content can be 0.5-6 weight portion, preferably 1-3 weight portion.
In the chromium inorganic agent of described metal surface, relative to the phosphonic acids complexing agent of every weight portion, with chromium element
Cubage, the content in trivalent chromium source can be 0.25-1.6 weight portion, preferably 0.5-1 weight portion.
In the chromium inorganic agent of described metal surface, relative to the phosphonic acids complexing agent of every weight portion, cilicon oxide filler
Content can be 3-8 weight portion, preferably 4.5-6.5 weight portion.
In the chromium inorganic agent of described metal surface, relative to the phosphonic acids complexing agent of every weight portion, water-soluble, film-forming
The content of 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 metal surface chromium inorganic agent is formed, preferable case further
Under, in the chromium inorganic agent of described metal surface, the content of phosphonic acids complexing agent is 5-15g/L, and, relatively
In the phosphonic acids complexing agent of every weight portion, the content of polycarboxylic acids aqueous dispersion is 0.8-1.2 weight portion, phosphorus
The content of acid dihydride aluminium 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.
Under preferable case, the alkali metal salt of described ATMP be ATMP four sodium,
At least one in ATMP five sodium and ATMP potassium.
Wherein, described polycarboxylic acids aqueous dispersion can be the polycarboxylic acids material with ion chelating capacity,
Such as poly-aspartate or poly (sodium aspartate), under preferable case, described polycarboxylic acids aqueous dispersion is poly-
In acrylic acid aqueous dispersant, Sodium Polyacrylate aqueous dispersion and HPMA at least one
Kind.Described polyacrylic acid aqueous dispersion can be the product meeting GB/T10533-2000；Described poly-
PAA aqueous dispersion can be the product meeting GB/T2838-2010；The poly-Malaysia of described hydrolysis
Acid anhydrides can be the product meeting GB/T10535-1997；Described poly-aspartate or poly (sodium aspartate)
It can be the product meeting HG/T3822-2006.Content and/or the consumption of polycarboxylic acids aqueous dispersion are
Calculate with solid.Solid is with for calculating or representing that the solid implication of solid content is identical herein, is poly-
Carboxylic acid aqueous dispersion is remaining composition after removing solvent.
Wherein, described trivalent chromium source can be Cr (OH)3, chromium sulfate, chromic nitrate, chromium phosphate, phosphoric acid
Dihydro chromium, chromium trichloride, chromic acetate, chromic tartrate, chromium+oxalic acid, chromium citrate, chromium gluconate and
At least one in maleic acid chromium.
In the present invention, described cilicon oxide filler does not has special requirement, can be based on silica
Various fillers, such as, described cilicon oxide filler can be nano-silica powder and/or nano silicon
Colloidal sol；Under preferable case, the particle diameter of the silica in described cilicon oxide filler can be 5-90nm, more
Be preferably 5-30nm, it is, for example possible to use purchased from the trade mark of Asahi Denka Co., Ltd. be AT-30,
The commercially available product of AT-30S, AT-40, AT-30A and AT-20, or limited purchased from Shandong Bai Te new material
The trade mark of company is the commercially available product of SS-25 and SS-30.Further, the content of cilicon oxide filler and/or consumption
Being to calculate with the weight of silica itself, the consumption of such as nano silicon dioxide sol is with in colloidal sol
The amount of silica calculates, and is i.e. multiplied by its dioxide-containing silica hundred with the weight of nano silicon dioxide sol
The numerical computations obtained after mark (weight).
In the present invention, described water-soluble film-forming resin can be various water miscible and can be used in film forming
Modified or unmodified resin, described resin can use with suitable object form, such as water-soluble
At least one in emulsion, water-soluble solution and water-soluble solid, the present invention not particularly requirement, only
Film forming be can be used in, such as, described water-soluble film-forming resin can be water-soluble polyester film forming tree
(i.e. water-soluble film-forming resin obtained by polyalcohols monomer and polynary acrylic monomer are polymerized, such as, purchase fat
From Guangzhou Lapo Fine Chemicals Co., Ltd., the polyester resin of trade mark CB2200), water-soluble phenylpropyl alcohol becomes
Film resin (i.e. water-soluble, film-forming tree obtained by styrene monomer and acrylic acid (ester) class monomer are polymerized
Fat, such as purchased from Guangzhou Chao Long Chemical Industry Science Co., Ltd, the trade mark is the styrene-acrylic emulsion of xy-108b),
Soluble epoxide film-forming resin (i.e. water-soluble film-forming resin obtained by the monomer containing epoxy radicals is polymerized,
Such as purchased from Dongguan City Heima Chemical Co., Ltd., the trade mark is the epoxy resin of BH620), water-soluble poly
Urethane film-forming resin (is i.e. polymerized by multicomponent isocyanate class monomer and multi-hydroxy compounds monomer and is obtained
Water-soluble film-forming resin, 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 is (i.e. obtained by silicone monomer and acrylic acid (ester) class monomer are polymerized
Water-soluble film-forming resin, such as Qingdao are made the country prosperous paint company TC-05 type silicone acrylic emulsion, and solid content is 48
Weight %), water-soluble acrylic film-forming resin (i.e. by acrylic acid (ester) class monomer polymerization obtained by water
Dissolubility film-forming resin, such as purchased from the acrylic resin that the trade mark is A-3418 of Guangzhou Ou Peng chemical industry) and
Water-soluble fluorine carbon film-forming resin (i.e. by water-soluble film-forming resin obtained by the polymerization of fluorinated monomer, such as, is purchased
From Beijing Shouchuang Nano Techn Co., Ltd., the trade mark is the water-base fluorocarbon emulsion of SKFT-I) at least
A kind of；Under preferable case, described water-soluble film-forming resin is water-soluble phenylpropyl alcohol film-forming resin, water-soluble ring
Oxygen film-forming resin, water-soluble silicon the third film-forming resin, water-soluble acrylic film-forming resin, soluble polyurethane
At least one in film-forming resin and water-soluble polyester film-forming resin.It is highly preferred that described water-soluble, film-forming
Resin is water-soluble phenylpropyl alcohol film-forming resin and/or water-soluble fluorine carbon film-forming resin.Containing of water-soluble film-forming resin
Amount and/or consumption calculate with solid.Solid and the solid implication for calculating or represent solid content herein
Identical, it is water-soluble film-forming resin and removes remaining composition after solvent.
Wherein, under preferable case, described metal surface chromium inorganic agent is possibly together with sodium phosphate, relative to often weighing
The phosphonic acids complexing agent of amount part, 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, permissible
Method in reference literature CN101608073B prepares trivalent chromium source.
On the other hand, present invention also offers a kind of method preparing metal surface chromium inorganic agent, wherein,
The method includes: (1) prepares the first solution, and described first solution contains phosphonic acids complexing agent, polycarboxylic acids water
Property dispersant and aluminium dihydrogen phosphate；Described phosphonic acids complexing agent is ATMP and/or amino three methene
The alkali metal salt of phosphonic acids；(2) preparing the second solution, described second solution contains trivalent chromium source, nanometer two
Silica, water-soluble film-forming resin；(3) described first solution and the second solution are mixed.
Wherein, in the method, relative to the phosphonic acids complexing agent of every weight portion, polycarboxylic acids aqueous dispersion
Consumption can be 0.5-2 weight portion, preferably 0.8-1.2 weight portion.
Wherein, in the method, relative to the phosphonic acids complexing agent of every weight portion, the consumption of aluminium dihydrogen phosphate can
Think 0.5-6 weight portion, preferably 1-3 weight portion.
Wherein, in the method, relative to the phosphonic acids complexing 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, preferably 0.5-1 weight portion.
Wherein, in the method, relative to the phosphonic acids complexing agent of every weight portion, the consumption of cilicon oxide filler can
Think 3-8 weight portion, preferably 4.5-6.5 weight portion.
Wherein, in the method, relative to the phosphonic acids complexing agent of every weight portion, the use of water-soluble film-forming resin
Amount can be 3-10 weight portion；It is preferably 5.5-7.5 weight portion.
Wherein, in the method, can be made in the chromium inorganic agent of metal surface by the addition of regulation water
The consumption of phosphonic acids complexing agent is 3-18g/L；It is preferably 5-15g/L.Can select the first solution, second
At least one in the mixture of solution and the first solution and the second solution regulates the addition of water.
Under preferable case, in the first solution, the content of phosphonic acids complexing agent is 10-30 weight %.Preferably feelings
Under condition, 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 metal surface chromium inorganic agent is formed, preferable case further
Under, relative to the phosphonic acids complexing agent of every weight portion, the consumption of polycarboxylic acids aqueous dispersion is 0.8-1.2 weight
Amount part, the consumption of aluminium dihydrogen phosphate is 1-3 weight portion, with the cubage of chromium element, trivalent chromium source
Consumption is 0.5-1 weight portion, and the consumption of cilicon oxide filler is 4.5-6.5 weight portion, water-soluble film-forming resin
Consumption be 5.5-7.5 weight portion, and, by the addition of regulation water, metal surface chromium is processed
The content of the phosphonic acids complexing agent in agent is 5-15g/L.
Under preferable case, described ATMP four sodium, ATMP five sodium and amino three
At least one in methylenephosphonic acid potassium.Wherein, described polycarboxylic acids aqueous dispersion can be to have ion chela
The polycarboxylic acids material of conjunction ability, such as poly-aspartate or poly (sodium aspartate), under preferable case, described
Polycarboxylic acids aqueous dispersion is that polyacrylic acid aqueous dispersion, Sodium Polyacrylate aqueous dispersion and hydrolysis are poly-
At least one in maleic anhydride.Described polyacrylic acid aqueous dispersion can be to meet GB
The product of/T10533-2000；Described Sodium Polyacrylate aqueous dispersion can be to meet GB/T
The product of 2838-2010；Described HPMA can be the product meeting GB/T10535-1997
Product；Described poly-aspartate or poly (sodium aspartate) can be the product meeting HG/T3822-2006.Poly-
Content and/or the consumption of carboxylic acid aqueous dispersion calculate with solid.Herein solid with for calculate or table
Show that the solid implication of solid content is identical, be remaining composition after polycarboxylic acids aqueous dispersion removes solvent.
Wherein, described trivalent chromium source can be Cr (OH)3, chromium sulfate, chromic nitrate, chromium phosphate, phosphoric acid
Dihydro chromium, chromium trichloride, chromic acetate, chromic tartrate, chromium+oxalic acid, chromium citrate, chromium gluconate and
At least one in maleic acid chromium.
In the present invention, described cilicon oxide filler does not has special requirement, can be based on silica
Various fillers, such as, described cilicon oxide filler can be nano-silica powder and/or nano silicon
Colloidal sol；Under preferable case, the particle diameter of the silica in described cilicon oxide filler can be 5-90nm, more
Be preferably 5-30nm, it is, for example possible to use purchased from the trade mark of Asahi Denka Co., Ltd. be AT-30,
The commercially available product of AT-30S, AT-40, AT-30A and AT-20, or limited purchased from Shandong Bai Te new material
The trade mark of company is the commercially available product of SS-25 and SS-30.Further, the content of cilicon oxide filler and/or consumption
Being to calculate with the weight of silica itself, the consumption of such as nano silicon dioxide sol is with in colloidal sol
The amount of silica calculates, and is i.e. multiplied by its dioxide-containing silica hundred with the weight of nano silicon dioxide sol
The numerical computations obtained after mark (weight).
In the present invention, described water-soluble film-forming resin can be various water miscible and can be used in film forming
Modified or unmodified resin, described resin can use with suitable object form, such as water-soluble
At least one in emulsion, water-soluble solution and water-soluble solid, the present invention not particularly requirement, only
Film forming be can be used in, such as, described water-soluble film-forming resin can be water-soluble polyester film forming tree
(i.e. water-soluble film-forming resin obtained by polyalcohols monomer and polynary acrylic monomer are polymerized, such as, purchase fat
From Guangzhou Lapo Fine Chemicals Co., Ltd., the polyester resin of trade mark CB2200), water-soluble phenylpropyl alcohol becomes
Film resin (i.e. water-soluble, film-forming tree obtained by styrene monomer and acrylic acid (ester) class monomer are polymerized
Fat, such as purchased from Guangzhou Chao Long Chemical Industry Science Co., Ltd, the trade mark is the styrene-acrylic emulsion of xy-108b),
Soluble epoxide film-forming resin (i.e. water-soluble film-forming resin obtained by the monomer containing epoxy radicals is polymerized,
Such as purchased from Dongguan City Heima Chemical Co., Ltd., the trade mark is the epoxy resin of BH620), water-soluble poly
Urethane film-forming resin (is i.e. polymerized by multicomponent isocyanate class monomer and multi-hydroxy compounds monomer and is obtained
Water-soluble film-forming resin, 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 is (i.e. obtained by silicone monomer and acrylic acid (ester) class monomer are polymerized
Water-soluble film-forming resin, such as Qingdao are made the country prosperous paint company TC-05 type silicone acrylic emulsion, and solid content is 48
Weight %), water-soluble acrylic film-forming resin (i.e. by acrylic acid (ester) class monomer polymerization obtained by water
Dissolubility film-forming resin, such as purchased from the acrylic resin that the trade mark is A-3418 of Guangzhou Ou Peng chemical industry) and
Water-soluble fluorine carbon film-forming resin (i.e. by water-soluble film-forming resin obtained by the polymerization of fluorinated monomer, such as, is purchased
From Beijing Shouchuang Nano Techn Co., Ltd., the trade mark is the water-base fluorocarbon emulsion of SKFT-I) at least
A kind of；Under preferable case, described water-soluble film-forming resin is water-soluble phenylpropyl alcohol film-forming resin, water-soluble ring
Oxygen film-forming resin, water-soluble silicon the third film-forming resin, water-soluble acrylic film-forming resin, soluble polyurethane
At least one in film-forming resin and water-soluble polyester film-forming resin.It is highly preferred that described water-soluble, film-forming
Resin is water-soluble phenylpropyl alcohol film-forming resin and/or water-soluble fluorine carbon film-forming resin.Containing of water-soluble film-forming resin
Amount and/or consumption calculate with solid.Solid and the solid implication for calculating or represent solid content herein
Identical, it is water-soluble film-forming resin and removes remaining composition after solvent.
Wherein, under preferable case, described second solution also has sodium phosphate, relative to the phosphonic acids of every weight portion
Complexing agent, the consumption of sodium phosphate is 0.5-4 weight portion, preferably 1-2 weight portion；Further, described three
Valency chromium source is obtained by reducing agent reduction of hexavalent chromium compound.Specifically, it is referred to document
Method in CN101608073B prepares trivalent chromium source.Obtained by reducing agent reduction of hexavalent chromium compound
During trivalent chromium source, the amount in trivalent chromium source calculates with hexavalent chromium compound.
On the other hand, present invention also offers the metal surface chromium prepared according to said method to process
Agent.
On the other hand, present invention also offers a kind of hot-dip metal plated material, this hot-dip metal plated material includes heat
Plating base material and the coating being attached on this hot-dip metal plated base material, described hot-dip metal plated base material is galvanizing
At least one in metal base, hot-dip aluminizing zinc metal base and hot-dip aluminizing zinc magnesium metal base material, its feature
Being, described coating is the cured product of metal surface as above chromium inorganic agent.
Wherein, the thickness of described coating can be the known thickness of passivating film on zinc-plating material, and the present invention does not has
Having particularly restriction, overweight coating then tack declines, and cover light then corrosion resistance declines, the most preferably
In the case of, 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 to described surface conditioning agent
On zinc-plated base material, being then dried, the temperature being dried 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, described surface conditioning agent is in unit are
Usage amount on zinc-plated base material can correspondingly adjust, such as, be 0.5-1.5 when the thickness requiring described coating
During 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 normal atmosphere pressure.
In the present invention, the solid content of various organic binders and viscosity and respectively according to standard GB/T/T
2793 and the GB/T1723 methods specified measure and record.
Hereinafter will be described the present invention by embodiment, but the scope of the present invention will be not limited to implement
In example.
Preparation embodiment 1
This prepares embodiment for illustrating that the method in reference literature CN101608073B passes through reducing agent
Reduction of hexavalent chromium compound obtains trivalent chromium source.
In the enamel reaction still of 3000 liters, add 300 kilograms of deionized waters, add 50 kilograms of chromic acid
Acid anhydride (CrO3), the agitator starting reactor stirs 10 minutes, makes chromic anhybride dissolve.Treat that chromic anhybride is complete
After CL, at room temperature add the citric acid of double centner, start rapidly agitator, make citric acid fast
Instant solution.When solution not effervescent, judge that reaction completes, and obtains required trivalent chromium source.
Embodiment 1
By the phosphonic acids complexing agent of 10g, (ATMP processes limited public affairs purchased from the calm and peaceful water in Shandong Province
Department, numbering CAS No.6419-19-8), (polyacrylic acid is purchased from the polycarboxylic acids aqueous dispersion of 10g
Shandong Taihe Water Treatment Co., Ltd., numbering CAS No.9003-01-4) and the biphosphate of 20g
Aluminium adds in 20g water, mixes to uniformly, obtain the first solution under the mixing speed of 1500 revs/min.
By the trivalent chromium source of 7g, (the trivalent chromium source that preparation embodiment 1 prepares, addition is with chromium unit
Element amount calculate), (nano silicon dioxide sol, purchased from Shandong Bai Te new material for the cilicon oxide filler of 56g
Co., Ltd, the trade mark is SS-30, and addition is in terms of silica), the water-soluble film-forming resin of 65g (by
(purchased from Guangzhou Chao Long Chemical Industry Science Co., Ltd, the trade mark is xy-108b phenylpropyl alcohol to the styrene-acrylic emulsion of equivalent
Emulsion, solid content is 48 weight %, and viscosity is 500-1000mPa s) and fluorine carbon emulsion (purchased from Beijing
Pioneering nanosecond science and technology Co., Ltd, the trade mark is the water-base fluorocarbon emulsion of SKFT-I, and solid content is 45 weights
Amount %, viscosity is 500-1000mPa s) composition) and 15g sodium phosphate addition 585g water in, 1500
Rev/min mixing speed under mix to uniformly, obtain the second solution.
Merge the first solution and the second solution, and be 1L with water adjustment volume, 1500 revs/min stir
Mix and mix to uniformly under speed, obtain uniform liquid.This uniform liquid is the metal surface of the present embodiment
Chromium inorganic agent.
Embodiment 2
By the phosphonic acids complexing agent of 10g, (ATMP five sodium processes purchased from the calm and peaceful water in Shandong Province and has
Limit company, numbering CAS No.2235-43-0), the polycarboxylic acids aqueous dispersion of 12g (Sodium Polyacrylate,
Purchased from Shandong Taihe Water Treatment Co., Ltd., numbering CAS No.9003-04-7) and the phosphoric acid of 10g
Aluminum dihydrogen adds in 30g water, mixes to uniformly, obtain first under the mixing speed of 1500 revs/min
Solution.
By the trivalent chromium source of 5g, (the trivalent chromium source that preparation embodiment 1 prepares, addition is with chromium unit
Element amount calculate), (nano silicon dioxide sol, purchased from Shandong Bai Te new material for the cilicon oxide filler of 65g
Co., Ltd, the trade mark is SS-30, and addition is in terms of silica), the water-soluble film-forming resin (fluorine of 75g
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 weight %, and viscosity is 500-1000mPa s)) and 10g sodium phosphate add in 570g water,
Mix under the mixing speed of 1500 revs/min to uniformly, obtain the second solution.
Merge the first solution and the second solution, and be 1L with water adjustment volume, 1500 revs/min stir
Mix and mix to uniformly under speed, obtain uniform liquid.This uniform liquid is the metal surface of the present embodiment
Chromium inorganic agent.
Embodiment 3
By the phosphonic acids complexing agent of 10g, (ATMP four sodium processes purchased from the calm and peaceful water in Shandong Province and has
Limit company, numbered CAS No.20592-85-2), the polycarboxylic acids aqueous dispersion of 8g (hydrolyze poly-horse
Carry out acid anhydrides, purchased from Shandong Taihe Water Treatment Co., Ltd., numbering CAS No.26099-09-02) and
The aluminium dihydrogen phosphate of 30g adds in 30g water, mixes to uniformly under the mixing speed of 1500 revs/min,
Obtain the first solution.
By the trivalent chromium source of 10g, (the trivalent chromium source that preparation embodiment 1 prepares, addition is with chromium unit
Element amount calculate), (nano silicon dioxide sol, purchased from Shandong Bai Te new material for the cilicon oxide filler of 45g
Co., Ltd, the trade mark is SS-30, and addition is in terms of silica), the water-soluble film-forming resin (benzene of 55g
Acrylic emulsion (purchased from Guangzhou Chao Long Chemical Industry Science Co., Ltd, the trade mark is xy-108b styrene-acrylic emulsion, Gu
Content is 48 weight %, and viscosity is 500-1000mPa s)) and 20g sodium phosphate add in 595g water,
Mix under the mixing speed of 1500 revs/min to uniformly, obtain the second solution.
Merge the first solution and the second solution, and be 1L with water adjustment volume, 1500 revs/min stir
Mix and mix to uniformly under speed, obtain uniform liquid.This uniform liquid is the metal surface of the present embodiment
Chromium inorganic agent.
Embodiment 4
By the phosphonic acids complexing agent of 10g, (ATMP processes limited public affairs purchased from the calm and peaceful water in Shandong Province
Department, numbering CAS No.6419-19-8), (polyacrylic acid is purchased from the polycarboxylic acids aqueous dispersion of 10g
Shandong Taihe Water Treatment Co., Ltd., numbering CAS No.9003-01-4) and the biphosphate of 20g
Aluminium adds in 20g water, mixes to uniformly, obtain the first solution under the mixing speed of 1500 revs/min.
By the trivalent chromium source (biphosphate chromium, addition calculates with the amount of chromium element) of 7g, the oxygen of 56g
SiClx filler (nano silicon dioxide sol, purchased from Shandong Bai Te new material Co., Ltd, the trade mark is SS-30,
Addition is in terms of silica), the water-soluble film-forming resin of 65g is (by the styrene-acrylic emulsion of equivalent (purchased from wide
Chao Long Chemical Industry Science Co., Ltd of state city, the trade mark is xy-108b styrene-acrylic emulsion, and solid content is 48 weight
%, viscosity is 500-1000mPa s) and fluorine carbon emulsion (purchased from Beijing Shouchuang Nano Techn Co., Ltd.,
The trade mark is the water-base fluorocarbon emulsion of SKFT-I, and solid content is 45 weight %, and viscosity is
500-1000mPa s) composition) add in 590g water, mix under the mixing speed of 1500 revs/min
To uniformly, obtain the second solution.
Merge the first solution and the second solution, and be 1L with water adjustment volume, 1500 revs/min stir
Mix and mix to uniformly under speed, obtain uniform liquid.This uniform liquid is the metal surface of the present embodiment
Chromium inorganic agent.
Embodiment 5
By the phosphonic acids complexing agent of 10g, (ATMP processes limited public affairs purchased from the calm and peaceful water in Shandong Province
Department, numbering CAS No.6419-19-8), (polyacrylic acid, purchased from mountain for the polycarboxylic acids aqueous dispersion of 5g
East saves calm and peaceful water and processes Co., Ltd, numbering CAS No.9003-01-4) and the aluminium dihydrogen phosphate of 60g
Add in 60g water, mix under the mixing speed of 1500 revs/min to uniformly, obtain the first solution.
By the trivalent chromium source of 16g, (the trivalent chromium source that preparation embodiment 1 prepares, addition is with chromium unit
Element amount calculate), (nano silicon dioxide sol, purchased from Shandong Bai Te new material for the cilicon oxide filler of 30g
Co., Ltd, the trade mark is SS-30, and addition is in terms of silica), the water-soluble film-forming resin of 30g (by
(purchased from Guangzhou Chao Long Chemical Industry Science Co., Ltd, the trade mark is xy-108b phenylpropyl alcohol to the styrene-acrylic emulsion of equivalent
Emulsion, solid content is 48 weight %, and viscosity is 500-1000mPa s) and fluorine carbon emulsion (purchased from Beijing
Pioneering nanosecond science and technology Co., Ltd, the trade mark is the water-base fluorocarbon emulsion of SKFT-I, and solid content is 45 weights
Amount %, viscosity is 500-1000mPa s) composition) and 15g sodium phosphate addition 560g water in, 1500
Rev/min mixing speed under mix to uniformly, obtain the second solution.
Merge the first solution and the second solution, and be 1L with water adjustment volume, 1500 revs/min stir
Mix and mix to uniformly under speed, obtain uniform liquid.This uniform liquid is the metal surface of the present embodiment
Chromium inorganic agent.
Embodiment 6
By the phosphonic acids complexing agent of 10g, (ATMP processes limited public affairs purchased from the calm and peaceful water in Shandong Province
Department, numbering CAS No.6419-19-8), (polyacrylic acid is purchased from the polycarboxylic acids aqueous dispersion of 20g
Shandong Taihe Water Treatment Co., Ltd., numbering CAS No.9003-01-4) and the aluminium dihydrogen phosphate of 5g
Add in 20g water, mix under the mixing speed of 1500 revs/min to uniformly, obtain the first solution.
By the trivalent chromium source of 2.5g, (the trivalent chromium source that preparation embodiment 1 prepares, addition is with chromium unit
Element amount calculate), (nano silicon dioxide sol, purchased from Shandong Bai Te new material for the cilicon oxide filler of 80g
Co., Ltd, the trade mark is SS-30, and addition is in terms of silica), the water-soluble film-forming resin of 100g
(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 %, and viscosity is 500-1000mPa s) and fluorine carbon emulsion (be purchased from
Beijing Shouchuang Nano Techn Co., Ltd., the trade mark is the water-base fluorocarbon emulsion of SKFT-I, and solid content is 45
Weight %, viscosity is 500-1000mPa s) composition) and 15g sodium phosphate addition 545g water in,
Mix under the mixing speed of 1500 revs/min to uniformly, obtain the second solution.
Merge the first solution and the second solution, and be 1L with water adjustment volume, 1500 revs/min stir
Mix and mix to uniformly under speed, obtain uniform liquid.This uniform liquid is the metal surface of the present embodiment
Chromium inorganic agent.
Embodiment 7
Prepare chromium ion passivating solution according to the method for embodiment 1, except for the difference that, use poly-aspartate
(PASP, purchased from Shandong Taihe Water Treatment Co., Ltd., numbering CAS No.181828-06-8) makees
For polycarboxylic acids aqueous dispersion.
Comparative example 1
Prepare metal surface chromium inorganic agent according to the method for embodiment 1, except for the difference that, use polyalcohol phosphorus
Acid esters (PAPE, purchased from Shandong Taihe Water Treatment Co., Ltd.) is as phosphonic acids complexing agent.
Comparative example 2
Metal surface chromium inorganic agent is prepared, except for the difference that, by phosphonic acids complexing agent according to the method for embodiment 1
Replace with phytic acid.
Preparation embodiment 2
The metal surface chromium inorganic agent 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, the weight on zinc 95 in zinc coat
Surface %), heated-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
Use XRF(XRF) measuring instrument measure numerical value.Wherein, the gold used during this prepares embodiment
Metal surface chromium inorganic agent be all prepared (i.e. obtaining uniform liquid) after store the metal surface of 1 day
Chromium inorganic agent.
Preparation embodiment 3-5
Galvanized steel plain sheet after processing according to the method preparation of preparation embodiment 2, except for the difference that, the gold of use
Metal surface chromium inorganic agent be all prepared (i.e. obtaining uniform liquid) after store 60,120 and 180
It metal surface chromium inorganic agent.
Testing example 1
By the requirement of regulation in GB/T101251997, carry out neutral salt spray test, measure system respectively
The galvanized steel plain sheet after the process of standby embodiment 2-5 corrosion resisting property after 400 DEG C of baking 30s.By " salt fog
Test 168h, corrosion area ＜ 3% " be considered as qualified.
Test result as above is as shown in table 1.Number of days in bracket represents metal surface chromium inorganic agent
The storage time.
Specify according to GB21275-2007 " regulated substance Cr VI detection method in electronic and electrical equipment "
Standard testing content of 6-valence Cr ions, result is listed in table 1(and only lists), content of 6-valence Cr ions less than 2ppm is
It is qualified to be considered as.
Table 1
From the data of table 1 it can be seen that the protecting film that formed of the metal surface chromium inorganic agent that the present invention provides
Corrosion resistance the most excellent, and the present invention provide metal surface chromium inorganic agent storage endurance the most very
Excellent.Further, the data according to table 1 are visible, and the content at preferred phosphonic acids complexing agent is 5-15g/L,
Further, relative to the phosphonic acids complexing agent of every weight portion, the content of polycarboxylic acids aqueous dispersion is 0.8-1.2
Weight portion, the content of aluminium dihydrogen phosphate is 1-3 weight portion, with the cubage of chromium element, trivalent chromium source
Content be 0.5-1 weight portion, the content of cilicon oxide filler is 4.5-6.5 weight portion, water-soluble, film-forming tree
In the case of the content of fat is 5.5-7.5 weight portion, it is possible to improve described metal surface chromium further and process
The corrosion resistance of the protecting film that agent is formed.Further, the data according to table 1 are visible, at preferred described polycarboxylic acids
Aqueous dispersion is polyacrylic acid aqueous dispersion, Sodium Polyacrylate aqueous dispersion and hydrolyzed polymaleic anhydride
In the case of at least one in acid anhydride, it is possible to improve the protecting film of described chromium formation further
Corrosion resistance.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
Execute the detail in mode, in the technology concept of the present invention, can be to the technical side of the present invention
Case carries out multiple simple variant, and these simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technology described in above-mentioned detailed description of the invention is special
Levy, in the case of reconcilable, can be combined by any suitable means, in order to avoid need not
The repetition wanted, various possible combinations are illustrated by the present invention the most separately.
Additionally, can also be combined between the various different embodiment of the present invention, as long as its
Without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. a metal surface chromium inorganic agent, described metal surface chromium inorganic agent contains water, phosphonic acids complexing
Agent, polycarboxylic acids aqueous dispersion, aluminium dihydrogen phosphate, trivalent chromium source, cilicon oxide filler, water-soluble, film-forming
Resin and sodium phosphate, described phosphonic acids complexing agent is ATMP four sodium or ATMP five
Sodium, the content of phosphonic acids complexing agent is 5-15g/L, and, relative to the phosphonic acids complexing agent of every weight portion,
The content of polycarboxylic acids aqueous dispersion is 0.8-1.2 weight portion, and 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, the content of cilicon oxide filler
For 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
For 0.5-4 weight portion.
Metal surface the most according to claim 1 chromium inorganic agent, wherein, described polycarboxylic acids is aqueous
Dispersant is in polyacrylic acid aqueous dispersion, Sodium Polyacrylate aqueous dispersion and HPMA
At least one；
Described trivalent chromium source is Cr (OH)3, chromium sulfate, chromic nitrate, chromium phosphate, biphosphate chromium, three
In chromium chloride, chromic acetate, chromic tartrate, chromium+oxalic acid, chromium citrate, chromium gluconate and maleic acid chromium
At least one；
Described cilicon oxide filler is nano-silica powder and/or nano silicon dioxide sol；
Described water-soluble film-forming resin is water-soluble polyester film-forming resin, water-soluble phenylpropyl alcohol film-forming resin, water
Dissolubility epoxy film forming resins, soluble polyurethane film-forming resin, water-soluble silicon the third film-forming resin, water solubility
At least one in acrylic acid film-forming resin and water-soluble fluorine carbon film-forming resin.
Metal surface the most according to claim 1 chromium inorganic agent, wherein, described trivalent chromium source is
Obtained by reducing agent reduction of hexavalent chromium compound.
Metal surface the most according to claim 1 chromium inorganic agent, wherein, relative to every weight portion
Phosphonic acids complexing agent, the content of sodium phosphate is 1-2 weight portion.
5. the method preparing metal surface chromium inorganic agent, it is characterised in that the method includes:
(1) preparing the first solution, described first solution contains phosphonic acids complexing agent, polycarboxylic acids aqueous dispersion
Agent and aluminium dihydrogen phosphate；Described phosphonic acids complexing agent is ATMP four sodium or ATMP
Five sodium；
(2) preparing the second solution, described second solution contains trivalent chromium source, nano silicon, water
Dissolubility film-forming resin；
(3) described first solution and the second solution are mixed；
Wherein, described second solution contains sodium phosphate, relative to the phosphonic acids complexing agent of every weight portion, poly-carboxylic
The consumption of acids dispersant is 0.8-1.2 weight portion, and the consumption of aluminium dihydrogen phosphate is 1-3 weight portion, with
The cubage of chromium element, the consumption in trivalent chromium source is 0.5-1 weight portion, and 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 consumption of sodium phosphate is
0.5-4 weight portion, and, make the phosphonic acids in the chromium inorganic agent of metal surface by the addition of regulation water
The content of complexing agent is 5-15g/L.
Method the most according to claim 5, wherein, described polycarboxylic acids aqueous dispersion is poly-third
At least one in olefin(e) acid aqueous dispersion, Sodium Polyacrylate aqueous dispersion and HPMA；
Described trivalent chromium source is Cr (OH)3, chromium sulfate, chromic nitrate, chromium phosphate, biphosphate chromium, three
In chromium chloride, chromic acetate, chromic tartrate, chromium+oxalic acid, chromium citrate, chromium gluconate and maleic acid chromium
At least one；
Described cilicon oxide filler is nano-silica powder and/or nano silicon dioxide sol；
Described water-soluble film-forming resin is water-soluble polyester film-forming resin, water-soluble phenylpropyl alcohol film-forming resin, water
Dissolubility epoxy film forming resins, soluble polyurethane film-forming resin, water-soluble silicon the third film-forming resin, water solubility
At least one in acrylic acid film-forming resin and water-soluble fluorine carbon film-forming resin.
Method the most according to claim 5, wherein, described trivalent chromium source is by reducing agent also
Former hexavalent chromium compound obtains.
Method the most according to claim 5, wherein, relative to the phosphonic acids complexing agent of every weight portion,
The consumption of sodium phosphate is 1-2 weight portion.
9. the metal surface chromium inorganic agent 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 is attached to this
Coating on hot-dip metal plated base material, described hot-dip metal plated base material is galvanizing metal base, hot-dip aluminizing zinc gold
Belong at least one in base material and hot-dip aluminizing zinc magnesium metal base material, it is characterised in that described coating is right
Require in 1-4 and 9 cured product of metal surface chromium inorganic agent described in any one.
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| CN106283009B (en) * | 2016-08-12 | 2019-03-19 | 攀钢集团攀枝花钢铁研究院有限公司 | Heat zinc coating plate coating solution and its preparation and application |
| KR20200081415A (en) * | 2017-10-30 | 2020-07-07 | 벌크 케미컬스, 인코포레이티드 | Process and composition for treating metal surfaces using 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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| CN1112601A (en) * | 1995-05-08 | 1995-11-29 | 化学工业部北京化工研究院 | Corrosion inhibitor for refrigerating fluid |
| 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 |
| CN102477551A (en) * | 2010-11-29 | 2012-05-30 | 攀钢集团钢铁钒钛股份有限公司 | Surface treatment agent and zinc-plating material |
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| CN102011112B (en) * | 2010-12-15 | 2012-11-28 | 济南德锡科技有限公司 | Zinc and zinc alloy plating black passivation solution and preparation method thereof |
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| CN1112601A (en) * | 1995-05-08 | 1995-11-29 | 化学工业部北京化工研究院 | Corrosion inhibitor for refrigerating fluid |
| 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 |
| CN102477551A (en) * | 2010-11-29 | 2012-05-30 | 攀钢集团钢铁钒钛股份有限公司 | Surface treatment agent and zinc-plating material |
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