CN101693811B - Chromium-free waterborne corrosion resistant coating used for surface of metal and preparation method thereof - Google Patents
Chromium-free waterborne corrosion resistant coating used for surface of metal and preparation method thereof Download PDFInfo
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- CN101693811B CN101693811B CN2009100356091A CN200910035609A CN101693811B CN 101693811 B CN101693811 B CN 101693811B CN 2009100356091 A CN2009100356091 A CN 2009100356091A CN 200910035609 A CN200910035609 A CN 200910035609A CN 101693811 B CN101693811 B CN 101693811B
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Abstract
The invention relates to a chromium-free waterborne corrosion resistant coating for the surface of metal and a preparation method thereof. The chromium-free waterborne corrosion resistant coating comprises the following components in percentage by mass: 15-33 flaked zinc powder, 2.5-8 flaked aluminium powder, 13.5-24 solvent, 0.2-2.5 assistant, 14-22 first silane coupling agent, 2-6 second silane coupling agent, 0.05-1.5 nano SiO2,0.03-1.2 nano TiO2, 0.02-1.5 nano ZrO2, 0.3-1 silver salt, 0.1-0.3 polyaniline, 0-0.6 tackifier and the balance of H2O, wherein the first silane coupling agent is a bi-[Gamma-(triethoxysilane) propyl] tetrasulfide; and the second silane coupling agent is a Gamma-aminopropyltriethoxysilane or Gamma-methacryloxypropyl trimethoxysilane. The coating contains no chromium and has corrosion resistance according with an international newest metal surface corrosion prevention technology.
Description
Technical field
The present invention relates to a kind of chromium-free waterborne corrosion resistant coating that is used for the metallic surface and preparation method thereof.
Background technology
Traditional dacro solution paint contains sexavalent chrome in its coating, and sexavalent chrome chance water can parse during use, corrosion resistance of coating is descended, and environment and human body are damaged.Stipulate among the 2000/53/EG of Europe that from July 1st, 2003, at the automobile of European production and selling, chromic content must not surpass 2 grams in each automobile.Therefore, develop a kind of green environmental protection technique abroad again and be called for short Ji Aomi (Geomet) technology.But monopolized by international transnational company always.For domestic automobile is gone abroad, be badly in need of exploitation a kind of have independent intellectual property right, performance and the suitable coating products of Ji Aomi (Geomet) technology.
Summary of the invention
First purpose of the present invention is: a kind of chromium-free waterborne corrosion resistant coating that is used for the metallic surface is provided, and its non-corrosibility and Ji Aomi (Geomet) technology is suitable, compliance with environmental protection requirements.
The technical scheme that realizes first purpose of the present invention is: a kind of chromium-free waterborne corrosion resistant coating that is used for the metallic surface, it is characterized in that, and the content of each component in coating, % counts with quality:
Zinc flake 15～33, flake aluminum 2.5～8, solvent 13.5～24,0.2～2.5, first kind of silane coupling agent 14～22 of auxiliary agent, second kind of silane coupling agent 2～6, nanometer SiO
20.05～1.5, nano-TiO
20.03～1.2, nanometer ZrO
20.02～1.5, silver salt 0.3～1, polyaniline 0.1～0.3, tackifier 0～0.6, H
2O is a surplus;
Described first kind of silane coupling agent is two-[γ-(triethoxysilicane) propyl group] tetrasulfide;
Described second kind of silane coupling agent is γ-An Bingjisanyiyangjiguiwan, perhaps is γ-methacryloxypropyl trimethoxy silane.
In the above-mentioned coating, described solvent is one or more in dipropylene glycol, Isopropanediol, the glycerol; Described auxiliary agent is emulsifying agent and wetting agent.
In the above-mentioned coating, described nanometer SiO
2Be powder dewatering nano SiO
2, its particle size range is 7～12nm; Nano-TiO
2Be powder acidity nanometer TiO
2, its particle size range is 10～20nm; Nanometer ZrO
2Be powder, its particle size range is 9～20nm.
Second purpose of the present invention is: provide a kind of simple to operate, the preparation method of the chromium-free waterborne corrosion resistant coating that is used for the metallic surface of constant product quality.
The technical scheme that realizes second purpose of the present invention is: a kind ofly prepare the above-mentioned method that is used for the chromium-free waterborne corrosion resistant coating of metallic surface, it is characterized in that concrete preparation process is as follows:
1. prepare raw material by the quality % content of each component in coating:
Zinc flake 15～33, flake aluminum 2.5～8, solvent 13.5～24,0.2～2.5, first kind of silane coupling agent 14～22 of auxiliary agent, second kind of silane coupling agent 2～6, nanometer SiO
20.05～1.5, nano-TiO
20.03～1.2, nanometer ZrO
20.02～1.5, silver salt 0.3～1, polyaniline 0.1～0.3, tackifier 0～0.6, H
2O is a surplus;
2. prepare the A component
Earlier solvent and auxiliary agent are added in the reactor, the back that stirs adds zinc flake and flake aluminum, and it is wetting to make it emulsification with speed stirring 0.5～2h of 300～700 rev/mins, leaves standstill 1.5～2h slaking then, makes soup compound, and discharging is the A component;
3. prepare the B component
Earlier with H
2O adds in the reactor, and stirring and regulating pH down is 5～7.5, adds nanometer SiO then
2, nano-TiO
2, nanometer ZrO
2, silver salt, polyaniline, first kind of silane coupling agent, second kind of silane coupling agent, stir 1.5～4h with 150～450 rev/mins speed and make two kinds of silane coupling agent hydrolysis, place 1.5～7h slaking then, make transparence liquid, discharging is the B component;
4. prepare coating
The B component transparent liquid that 3. A component soup compound that 2. step is made and step make adds in the reactor, mixes, stirs 8～12h, and discharging, packing are the chromium-free waterborne corrosion resistant coating that the present invention is used for the metallic surface;
The B component transparent liquid that 3. A component soup compound that perhaps 2. step is made and step make adds in the reactor, mix, stir 8～12h, then tackifier are added in the reactor, mix, stir 8～14h, the discharging packing is the chromium-free waterborne corrosion resistant coating that the present invention is used for the metallic surface.
Among the above-mentioned preparation method, described first kind of silane coupling agent is two-[γ-(triethoxysilicane) propyl group] tetrasulfide; Described second kind of silane coupling agent is γ-An Bingjisanyiyangjiguiwan, perhaps is γ-methacryloxypropyl trimethoxy silane; Described nanometer SiO
2Be powder dewatering nano SiO
2, its particle size range is 7～12nm; Nano-TiO
2Be powder acidity nanometer TiO
2, its particle size range is 10～20nm; Nanometer ZrO
2Its diameter of particle scope is 9～20nm.
Among the above-mentioned preparation method, described solvent is one or more in dipropylene glycol, Isopropanediol, the glycerol; Described auxiliary agent is emulsifying agent and wetting agent.
Technique effect of the present invention is: 1. the coating of technical solution of the present invention is allocated the nano material SiO of proper amt again into owing to allocate an amount of zinc flake into and the main corrosion-inhibiting pigment of flake aluminum conduct
2, TiO
2, ZrO
2, by proper assistant, make zinc flake and flake aluminum be arranged in parallel in coating, metal base is formed laminated shield, and nano material SiO
2, TiO
2, ZrO
2Be distributed in the density that has increased coating in its gap, more strengthened shielding effect; The polyaniline that is added is owing to have the metal base of reduction electropotential, make metal be difficult for losing the function of electronics, thereby the salt spray resistance ability of filming is improved greatly, therefore, coating of the present invention need not the rust-stabilising pigment that uses tradition to contain chromium or contain other poisonous metals, do not have waste residue, waste water and exhaust gas emission in production and use, realize cleaner production; Again because coating of the present invention is to form the oligopolymer of silicon as film forming matter with two kinds of silane coupling agents through hydrolytic polymerization, the Si-O-Si key that this film forming matter contains has strengthened and has been coated with film heat resistance, the multiple group that film forming matter contains has increased the sticking power of filming with metallic substrate surface, therefore, coating Chrome-free of the present invention and anti-corrosion capability are suitable with external like product, have also saved a large amount of foreign exchanges; 2. the concrete operations that the preparation method provided of technical solution of the present invention can guarantee zinc flake and flake aluminum and nano material SiO
2, TiO
2, ZrO
2Be evenly distributed on the effect that makes in the film forming matter separately and obtain performance, guarantee that also two kinds of silane coupling agents finish hydrolysis, stable storage period at coating products, and under sintering condition, can carry out effective polymerization film formation, formation has the coating of anticorrosion with coat erosion function of the present invention, the effect of film forming matter is not fully exerted, and simple to operately, easy to control guarantees constant product quality.
Embodiment
Below in conjunction with embodiment the present invention is described specifically, but not limited.The raw material that embodiment uses unless otherwise indicated is the coating industrial goods, all can buy from market.
The present invention is used for the chromium-free waterborne corrosion resistant coating of metallic surface, the quality % content of its each component in coating is as follows: zinc flake 15～33, flake aluminum 2.5～8, solvent 13.5～24,0.2～2.5, first kind of silane coupling agent 14～22 of auxiliary agent, second kind of silane coupling agent 2～6, nanometer SiO
20.05～1.5, nano-TiO
20.03～1.2, nanometer ZrO
20.02～1.5, silver salt 0.3～1, polyaniline 0.1～0.3, tackifier 0～0.6, H
2O is a surplus.
Embodiment 1
1. press the concrete prescription of table 1 and prepare raw material:
Table 1
| Component | Material name, specification | Consumption, quality % |
| Zinc flake | Long 15～18 μ m, thick 0.1～0.2 μ m | 22 |
| Flake aluminum | Long 15～18 μ m, thick 0.1～0.2 μ m | 5 |
| Solvent | Dipropylene glycol | 13.5 |
| Auxiliary agent emulsifying agent wetting agent | TX-10 JFC | 1.5 1.0 |
| First kind of silane coupling agent | Si-69 | 18 |
| Second kind of silane coupling agent | A-174 | 6 |
| Nanometer SiO 2 | Granularity 7～12nm | 0.24 |
| Nano-TiO 2 | Granularity 10～20nm; | 0.12 |
| Nanometer ZrO 2 | Granularity 9～20nm | 0.10 |
| Silver salt | AgNO 3 | 0.60 |
| Polyaniline | Polyaniline | 0.18 |
| Tackifier | ?HEC | 0 |
| Water | Complement to 100 |
Annotate: the polyoxyethylene nonylphenol ether nonionic emulsifier product grade that TX-10 produces for the Xingtai City auxiliary reagent factory; JFC is the product grade in outstanding chemical plant, sea, Zibo; A-174 is γ-methacryloxypropyl trimethoxy silane product grade that the flourish chemical plant of Qufu China produces; Si-69 is two-[γ-(triethoxysilicane) propyl group] tetrasulfide product grade that German goldschmidt chemical corporation is produced; HEC is the product grade of the Natvosol of Guangzhou fine horse person of outstanding talent trading company production;
2. prepare the A component
Earlier solvent and auxiliary agent are added in the reactor, the back that stirs adds zinc flake and flake aluminum, and it is wetting to make it emulsification with speed stirring 0.5～2h of 180～450 rev/mins, leaves standstill 1.5～2h slaking then, makes soup compound, and discharging is the A component;
3. prepare the B component
Earlier with H
2O adds in the reactor, stirs to add Li down
2CO
3Or ZnO to regulate pH be 5～7.5, add nanometer SiO then
2, nano-TiO
2, nanometer ZrO
2, silver salt, polyaniline, first kind of silane coupling agent, second kind of silane coupling agent, stir 2.5h with 400 rev/mins speed and make two kinds of silane coupling agent hydrolysis, place 1.5～7h slaking then, make transparence liquid, discharging is the B component;
4. prepare coating
The B component transparent liquid that 3. A component soup compound that 2. step is made and step make adds in the reactor, mixes, stirs 8～12h, and discharging, packing are the chromium-free waterborne corrosion resistant coating that the present invention is used for the metallic surface.
Embodiment 2
1. press the concrete prescription of table 2 and prepare raw material:
Table 2
| Component | Material name, specification | Consumption, quality % |
| Zinc flake | Long 15～18 μ m, thick 0.1～0.2 μ m | 25 |
| Flake aluminum | Long 15～18 μ m, thick 0.1～0.2 μ m | 5 |
| Solvent | Isopropanediol | 18 |
| Auxiliary agent emulsifying agent wetting agent | The TX-10 polyoxyethylene glycol | 0.6 0.8 |
| First kind of silane coupling agent | Si-69 | 22 |
| Second kind of silane coupling agent | KH-550 | 3 |
| Nanometer SiO 2 | Granularity 7～12nm | 0.12 |
| Nano-TiO 2 | Granularity 10～20nm; | 0.08 |
| Nanometer ZrO 2 | Granularity 9～20nm | 0.10 |
| Silver salt | AgNO 3 | 0.60 |
| Polyaniline | Polyaniline | 0.24 |
| Tackifier | HEC | 0.35 |
| Water | Complement to 100 |
Annotate: the γ-An Bingjisanyiyangjiguiwan product grade that KH-550 produces for U.S.'s union carbide corporation;
It is identical with embodiment 1 with the operation that 3. step prepares the B component that 2. step prepares the A component;
4. prepare coating
The B component transparent liquid that 3. A component soup compound that 2. step is made and step make adds in the reactor, mix, stir 8～12h, then tackifier are added in the reactor, mix, stir 8～14h, the discharging packing is the chromium-free waterborne corrosion resistant coating that the present invention is used for the metallic surface.
Coating property of the present invention detects
Double thread part and non-threaded fastener apply (spraying or brush) respectively with chromium-free waterborne corrosion resistant coating of the present invention (embodiment 1 and embodiment 2) and external Ji Aomi (Geomet) product, solidifying the back coating thickness is 8～10 μ m, carry out salt-fog resistant test according to the method for GB/T18686-2002 then, the result is as follows:
The salt fog resistance of the thread part that applies with chromium-free waterborne corrosion resistant coating of the present invention (embodiment 1 and embodiment 2) all reaches 480h and red rust do not occur, thread part with chromium-free waterborne corrosion resistant coating of the present invention (embodiment 1 and embodiment 2) coating, again behind the use silicon coating sealing treatment, red rust did not appear in 720 hours;
The salt fog resistance of the non-threaded fastener that applies with chromium-free waterborne corrosion resistant coating of the present invention (embodiment 1 and embodiment 2) all reaches 1000h and red rust do not occur;
The salt fog resistance of the thread part that applies with external Ji Aomi (Geomet) product all reaches 480h and red rust do not occur; The salt fog resistance of non-threaded fastener all reaches 1000h and red rust do not occur.
Detected result shows to have stronger salt fog resistance performance after metal (especially ferrous metal) surface-coated chromium-free waterborne corrosion resistant of the present invention is coated with, and outward appearance better, more stable.Up-to-date metallic surface, alternative world aseptic technic (Geomet technology), the automobile component enterprise that exports for China provides technical guarantee service cheaply, for enterprise saves a large sum of foreign exchange expenditure.
Coating of the present invention can be applicable to the zinc alloy coating floor height protection against corrosion field of automobile component (as brake flange, wheel hub, bolt, engine bolt etc.), high-speed railway, track traffic, bridge connection component.
Claims (6)
1. a chromium-free waterborne corrosion resistant coating that is used for the metallic surface is characterized in that, the content of each component in coating, and % counts with quality:
Zinc flake 15～33, flake aluminum 2.5～8, solvent 13.5～24,0.2～2.5, first kind of silane coupling agent 14～22 of auxiliary agent, second kind of silane coupling agent 2～6, nanometer SiO
20.05～1.5, nano-TiO
20.03～1.2, nanometer ZrO
20.02～1.5, silver salt 0.3～1, polyaniline 0.1～0.3, tackifier 0～0.6, H
2O is a surplus;
Described first kind of silane coupling agent is two-[γ-(triethoxysilicane) propyl group] tetrasulfide;
Described second kind of silane coupling agent is γ-An Bingjisanyiyangjiguiwan, perhaps is γ-methacryloxypropyl trimethoxy silane.
2. coating according to claim 1 is characterized in that, described solvent is one or more in dipropylene glycol, Isopropanediol, the glycerol; Described auxiliary agent is emulsifying agent and wetting agent.
3. coating according to claim 1 is characterized in that, described nanometer SiO
2Be powder dewatering nano SiO
2, its particle size range is 7～12nm; Nano-TiO
2Be powder acidity nanometer TiO
2, its particle size range is 10～20nm; Nanometer ZrO
2Be powder, its particle size range is 9～20nm.
4. one kind prepares the method that claim 1 is used for the chromium-free waterborne corrosion resistant coating of metallic surface, it is characterized in that, concrete preparation process is as follows:
1. prepare raw material by the quality % content of each component in coating:
Zinc flake 15～33, flake aluminum 2.5～8, solvent 13.5～24,0.2～2.5, first kind of silane coupling agent 14～22 of auxiliary agent, second kind of silane coupling agent 2～6, nanometer SiO
20.05～1.5, nano-TiO
20.03～1.2, nanometer ZrO
20.02～1.5, silver salt 0.3～1, polyaniline 0.1～0.3, tackifier 0～0.6, H
2O is a surplus;
2. prepare the A component
Earlier solvent and auxiliary agent are added in the reactor, the back that stirs adds zinc flake and flake aluminum, and it is wetting to make it emulsification with speed stirring 0.5～2h of 300～700 rev/mins, leaves standstill 1.5～2h slaking then, makes soup compound, and discharging is the A component;
3. prepare the B component
Earlier with H
2O adds in the reactor, and stirring and regulating pH down is 5～7.5, adds nanometer SiO then
2, nano-TiO
2, nanometer ZrO
2, silver salt, polyaniline, first kind of silane coupling agent, second kind of silane coupling agent, stir 1.5～4h with 150～450 rev/mins speed and make two kinds of silane coupling agent hydrolysis, place 1.5～7h slaking then, make transparence liquid, discharging is the B component;
4. prepare coating
The B component transparent liquid that 3. A component soup compound that 2. step is made and step make adds in the reactor, mixes, stirs 8～12h, and discharging, packing are the chromium-free waterborne corrosion resistant coating that is used for the metallic surface;
The B component transparent liquid that 3. A component soup compound that perhaps 2. step is made and step make adds in the reactor, mix, stir 8～12h, then tackifier are added in the reactor, mix, stir 8～14h, the discharging packing is the chromium-free waterborne corrosion resistant coating that is used for the metallic surface.
5. preparation method according to claim 4 is characterized in that, described first kind of silane coupling agent is two-[γ-(triethoxysilicane) propyl group] tetrasulfide; Described second kind of silane coupling agent is γ-An Bingjisanyiyangjiguiwan, perhaps is γ-methacryloxypropyl trimethoxy silane; Described nanometer SiO
2Be powder dewatering nano SiO
2, its particle size range is 7～12nm; Nano-TiO
2Be powder acidity nanometer TiO
2, its particle size range is 10～20nm; Nanometer ZrO
2Its diameter of particle scope is 9～20nm.
6. preparation method according to claim 4 is characterized in that, described solvent is one or more in dipropylene glycol, Isopropanediol, the glycerol; Described auxiliary agent is emulsifying agent and wetting agent.
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|---|---|---|---|
| CN2009100356091A CN101693811B (en) | 2009-09-28 | 2009-09-28 | Chromium-free waterborne corrosion resistant coating used for surface of metal and preparation method thereof |
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|---|---|---|---|
| CN2009100356091A CN101693811B (en) | 2009-09-28 | 2009-09-28 | Chromium-free waterborne corrosion resistant coating used for surface of metal and preparation method thereof |
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| CN101693811B true CN101693811B (en) | 2011-09-07 |
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Families Citing this family (13)
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| CN101857737B (en) * | 2010-07-08 | 2012-03-21 | 内蒙古兴泰建筑有限责任公司 | Anticorrosive nanometer aqueous architectural coating and preparation method thereof |
| CN102086313B (en) * | 2010-11-04 | 2012-08-29 | 江苏麟龙新材料股份有限公司 | Magnesium-containing coating for marine climate-resistant anticorrosion treatment |
| CN103122157A (en) * | 2011-11-18 | 2013-05-29 | 攀钢集团研究院有限公司 | Metal protecting coating and hot-dipped metal material |
| US9028920B2 (en) | 2012-03-28 | 2015-05-12 | Dubois Chemicals, Inc. | Pretreatment of metal surfaces prior to paint using polyaniline particles |
| CN103031056B (en) * | 2012-12-18 | 2016-02-24 | 安徽六方重联机械股份有限公司 | A kind of Metal surface silane treatment agent containing water nano zinc oxide material and preparation method thereof |
| CN103059723A (en) * | 2012-12-18 | 2013-04-24 | 安徽六方重联机械股份有限公司 | Stripping-resistant metal surface silicane treating agent and preparation method thereof |
| CN103031057A (en) * | 2012-12-18 | 2013-04-10 | 安徽六方重联机械股份有限公司 | Metal surface silane treating agent containing plant ash and preparation method thereof |
| CN103045086B (en) * | 2012-12-18 | 2016-03-02 | 安徽六方重联机械股份有限公司 | A kind of Metal surface silane treatment agent and preparation method thereof |
| CN103254764A (en) * | 2013-04-08 | 2013-08-21 | 马鞍山拓锐金属表面技术有限公司 | Anti-stripping metal surface silane treatment agent and preparation method thereof |
| CN103254783B (en) * | 2013-04-08 | 2016-05-11 | 马鞍山拓锐金属表面技术有限公司 | A kind of aqueous surface-treating agent and preparation method thereof |
| CN104356938B (en) * | 2014-10-08 | 2017-01-25 | 沈阳市航达科技有限责任公司 | Chromium-free water-based metal anticorrosive paint and preparation method thereof |
| CN113843120A (en) * | 2021-09-23 | 2021-12-28 | 张朝辉 | Surface anticorrosion and antirust treatment process for antirust-free self-tapping screw |
| CN115093734A (en) * | 2022-04-28 | 2022-09-23 | 广东工业大学 | Preparation method of chromium-free Zn-Al paint |
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| CN1771351A (en) * | 2003-05-09 | 2006-05-10 | 德古萨公司 | Composition for coating metals to protect against corrosion |
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