CN106147564A - A kind of preparation method of Chrome-free anticorrosive paint - Google Patents
A kind of preparation method of Chrome-free anticorrosive paint Download PDFInfo
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- CN106147564A CN106147564A CN201510157124.5A CN201510157124A CN106147564A CN 106147564 A CN106147564 A CN 106147564A CN 201510157124 A CN201510157124 A CN 201510157124A CN 106147564 A CN106147564 A CN 106147564A
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Abstract
Present invention relates particularly to the preparation method of a kind of Chrome-free anticorrosive paint, its technical scheme is: first stir the flake zinc powder of 5 ~ 25wt% and the flakey aluminium powder of 5 ~ 15wt%, add the inorganic additive of organic solvent, the dispersant of 1.1 ~ 1.8wt%, the corrosion inhibiter of 3 ~ 8wt% and the 3 ~ 10wt% of 25 ~ 40wt%, stirring 20 ~ 40min, makes base-material.Then add in base-material after the organic solvent of the modified resin of 5 ~ 15wt%, the organo silane coupling agent of 1 ~ 3wt% and 25 ~ 30wt% being stirred, or stirring 30 ~ 50min, prepare chromium-free zinc aluminum anticorrosive paint；Or stirring 30 ~ 50min, add the hydroxyethyl cellulose of 0.05 ~ 0.5wt%, stirring 20 ~ 50min, prepare chromium-free zinc aluminum anticorrosive paint, the present invention has that environmental friendliness, energy consumption be little and the feature of low cost, and the obtained coating impact strength after chromium-free zinc aluminum anticorrosive paint coating is high, corrosion resistance is good, adhesion is strong and hardness is high.
Description
Technical field
The invention belongs to anticorrosive paint technical field, be specifically related to the preparation method of a kind of Chrome-free anticorrosive paint.
Background technology
Traditional electrogalvanizing and galvanizing technique due to corrosion resistance difference, energy consumption is big, seriously polluted, have hydrogen embrittlement, and uses temperature to be limited by passivating film aging temperature, can only be used below at 100 DEG C, have significant limitation.Aluminum Coating (Dacromet/steel) is owing to having traditional electrogalvanizing and the incomparable advantage of galvanizing, thus has obtained quite being widely applied in fields such as automobile, medicine, electric power, oil and military projects.Aluminum Coating is to be coated on surface of the work after the mixed liquor by zinc flake and aluminium powder, chromic anhydride, wetting agent, dispersant, deionized water and other auxiliary agents composition stirs, and then solidifies at 300 DEG C, and redox reaction forms unbodied nCr2O3·mCrO3Complex salt.
But, Aluminum Coating contains Cr6+, Cr6+It is well-known harmful substance, strong toxicity and have carcinogenesis, severe contamination can be caused to environment for human survival, the therefore use of chromium is limited by more and more stricter.Although the Cr of the overwhelming majority in zinc-chromium coating6+Change into Cr by reaction during baking film forming3+, but still have minimal amount of chromium to be retained in Aluminum Coating with the chromic form of solubility.Under normal circumstances, its molten amount should be not more than 3 μ g/cm2, even if being that this quantity has also equally exceeded 0.6 μ g/cm with Zincing passivation layer2This causes the limit of allergy.Europe 2000/53/EG regulation, from 1 day July in 2003, in each automobile of Europe production and selling, chromic content must not exceed 2g, does not allow containing Cr in the corrosion-inhibiting coating that automobile uses6+, in the automobile industry of industrially developed country, many brand vehicles also take the lead in having formulated the technical standard without chrome coating in the world.So the research and development not containing the aseptic technic of the poisonous metals such as Cr VI are just extremely urgent, there is considerable economic and social benefit.
The product achieving industrialization without chrome coating at present cans be counted on one's fingers: a kind of is Geomet (Geomet) coating released by MCI company of the U.S., a kind of Delta coating being Delta company of Germany and releasing, and the BNC aqueous chromium-free Aluminum Coating of Yongtai, Beijing and release.Though these coating eliminate the chromium in tradition Dacroment, but the weatherability of coating has all declined compared with tradition Dacroment with decay resistance, and must use with another layer of organic seal coat collocation, considerably increases coating cost.The patented technology of Zinc-aluminum composite plating coating and preparation method thereof (CN101074337A), uses zinc flake, flake aluminum, resinene, diluent, nonionic surfactant, antisettling agent and dispersant to make Zinc-aluminum composite plating coating.Owing to diluent employs toluene and the poisonous and hazardous organic solvent of dimethylbenzene, pollute environment.Although moreover its film layer has preferable adhesive force, but decay resistance is not high, hardness is not high, and thicknesses of layers is partially thick.The patented technology of a kind of chromium-free Dyclo paint (CN101260252A), the metal parts after coating is placed in 200～400 DEG C of solidifications, processes solidification temperature needed for technique high, and energy consumption is big.
Content of the invention
It is contemplated that overcome prior art defect, it is therefore an objective to provide a kind of environmental friendliness, energy consumption little and the preparation method of chromium-free zinc aluminum anticorrosive paint of low cost；With the coating impact strength after the chromium-free zinc aluminum anticorrosive paint coating prepared by the method is high, corrosion resistance is good, adhesion is strong and hardness is high.
The technical solution adopted in the present invention is: first stir the flake zinc powder of 5～25wt% and the flakey aluminium powder of 5～15wt%, add the inorganic additive of organic solvent, the dispersant of 1.1～1.8wt%, the corrosion inhibiter of 3～8wt% and the 3～10wt% of 25～40wt%, stirring 20～40min, makes base-material.
Add in base-material after the organic solvent of the modified resin of 5～15wt%, the organo silane coupling agent of 1～3wt% and 25～30wt% being stirred after probable, stir 30～50min, prepare chromium-free zinc aluminum anticorrosive paint；
Add in base-material after the organic solvent of the modified resin of 5～15wt%, the organo silane coupling agent of 1～3wt% and 25～30wt% being stirred after probable, stirring 30～50min, add the hydroxyethyl cellulose of 0.05～0.5wt%, stirring 20～50min, prepares chromium-free zinc aluminum anticorrosive paint.
In technique scheme: the piece footpath of flake zinc powder is 10～15 μm, thickness is 0.1～0.2 μm；The piece footpath of flakey aluminium powder is 10～12 μm, and thickness is 0.1～0.2 μm；Organic solvent is more than one in ethylene glycol ether acetate, butyl acetate, butyl methacrylate, dioctyl phthalate, acetone, cyclohexanone, MEK, isopropanol, n-butanol, ethylene glycol and propane diols, and more than one the organic solvent front and back adding twice is all identical；Dispersant is fatty alcohol polyethenoxy ether class；Corrosion inhibiter is thiocarbamide or is BTA；Inorganic additive is for the nano silicon through nanoscale microemulsion surface modification or for through the nanometer silicon carbide of nanoscale microemulsion surface modification；Modified resin is more than one in epoxy modified acrylic resin, polyurethane modified epoxy and epoxy modified phenolic resin；Organo silane coupling agent is the one in organo silane coupling agent KH-550, organo silane coupling agent KH-560, organo silane coupling agent KH-570 and organo silane coupling agent KH-900.
The present invention is carried out at normal temperatures, and technique is simple, the production time is short, reduces production cost；The binding agent being used is organo silane coupling agent and modified resin, rather than chromic anhydride, it is achieved that coating and coating entirely without chromaking, become real ecotypic environmental protection coating material；Organo silane coupling agent can react formation zinc-silicic acid-iron compound with the iron ion of the substrate surface such as steel, iron by alkylation, and also can react with the zinc ion on zinc powder minuteness particle surface, form one layer of hard film and be coated on the surface of minuteness particle, thus be bonded together with steel basic unit, substantially increase the adhesive force in metal surface for the coating and corrosion resistance；The inorganic additive being used is for the nano silicon through nanoscale microemulsion surface modification or for through the nanometer silicon carbide of nanoscale microemulsion surface modification, substantially increase hardness, scratch resistance, antifriction quality and the decay resistance of coating, significantly reduce the micro-crack that curing of coatings causes；Organic solvent in goods lower boiling solvent in belonging to, can be attached to metallic substrate surface 220 ± 10 DEG C of solidifications, less than the solidification temperature 300 DEG C of common process, is substantially reduced Energy in use, saves processing cost.
Made Chrome-free anticorrosive paint can reach the salt-fog resistant test of more than 480 hours under the thicknesses of layers of 15 μm, adhesive force reaches 5 grades, hardness reaches more than 5H, coating heat resistance (400 DEG C) is 20～30 hours, resistance to water (40 DEG C) is 240～280 hours, salt tolerance is 65～75 hours, and impact strength is 45～65kg cm
Therefore, the present invention has that environmental friendliness, energy consumption be little and the feature of low cost, and the obtained coating impact strength after chromium-free zinc aluminum anticorrosive paint coating is high, corrosion resistance is good, adhesion is strong and hardness is high.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the invention will be further described, not limiting of its scope:
In this embodiment: zinc powder is flake zinc powder, piece footpath is 10～15 μm, and thickness is 0.1～0.2 μm；Aluminium powder is flakey aluminium powder, and piece footpath is 10～12 μm, and thickness is 0.1～0.2 μm.Following example will not be repeated again.
Embodiment 1
The preparation method of a kind of Chrome-free anticorrosive paint: first the flake zinc powder of 5～10wt% and the flakey aluminium powder of 10～15wt% are stirred, add the nano silicon through nanoscale microemulsion surface modification of ethylene glycol ether acetate, the AEO AEO-3 of 1.5～1.8wt%, the thiocarbamide of 3～5wt% and the 5～10wt% of 30～40wt%, stirring 20～40min, makes base-material.Then add in base-material after the ethylene glycol ether acetate of the polyurethane modified epoxy of 8～15wt%, the organo silane coupling agent KH-550 of 1～3wt% and 25～30wt% being stirred, stirring 30～50min, add the hydroxyethyl cellulose of 0.05～0.5wt%, stirring 20～50min, prepares chromium-free zinc aluminum anticorrosive paint.
Chrome-free anticorrosive paint obtained by the present embodiment, coating after coating is after tested: hardness is 6H, adhesive force is 5 grades, salt-fog resistant test is 480～490 hours, salt tolerance is 65～68 hours, heat resistance (400 DEG C) is 20～24 hours, and resistance to water (40 DEG C) is 250～260 hours, and impact strength is 56～65kg cm.
Embodiment 2
The preparation method of a kind of Chrome-free anticorrosive paint: a kind of chromium-free zinc aluminum anticorrosive paint and preparation method: first the flake zinc powder of 5～10wt% and the flakey aluminium powder of 10～15wt% are stirred, add the nanometer silicon carbide through nanoscale microemulsion surface modification of cyclohexanone, the AEO AEO-4 of 1.5～1.8wt%, the thiocarbamide of 3～5wt% and the 5～10wt% of 30～40wt%, stirring 20～40min, makes base-material.Then add in base-material after the polyurethane modified epoxy of 8～15wt% and the cyclohexanone of epoxy modified phenolic resin, the organo silane coupling agent KH-560 of 1～3wt% and 25～30wt% being stirred, stirring 30～50min, add the hydroxyethyl cellulose of 0.05～0.5wt%, stirring 20～50min, prepares chromium-free zinc aluminum anticorrosive paint.
Chrome-free anticorrosive paint obtained by the present embodiment, coating after coating is after tested: hardness is 5H, adhesive force is 5 grades, salt-fog resistant test is 490～500 hours, salt tolerance is 67～70 hours, heat resistance (400 DEG C) is 25～30 hours, and resistance to water (40 DEG C) is 248～256 hours, and impact strength is 53～58kg cm.
Embodiment 3
The preparation method of a kind of Chrome-free anticorrosive paint: a kind of chromium-free zinc aluminum anticorrosive paint and preparation method: first the flake zinc powder of 5～10wt% and the flakey aluminium powder of 10～15wt% are stirred, add the ethylene glycol ether acetate of 30～40wt% and the nano silicon through nanoscale microemulsion surface modification of acetone, the AEO AEO-5 of 1.5～1.8wt%, the BTA of 3～5wt% and 5～10wt%, stirring 20～40min, makes base-material.Then add in base-material after the polyurethane modified epoxy of 8～15wt%, the ethylene glycol ether acetate of the organo silane coupling agent KH-570 of 1～3wt% and 25～30wt% and acetone being stirred, stirring 30～50min, add the hydroxyethyl cellulose of 0.05～0.5wt%, stirring 20～50min, prepares chromium-free zinc aluminum anticorrosive paint.
Chrome-free anticorrosive paint obtained by the present embodiment, coating after coating is after tested: hardness is 6H, adhesive force is 5 grades, salt-fog resistant test is 482～490 hours, salt tolerance is 65～69 hours, heat resistance (400 DEG C) is 20～23 hours, and resistance to water (40 DEG C) is 244～253 hours, and impact strength is 55～65kg cm.
Claims (10)
1. the preparation method of a Chrome-free anticorrosive paint, it is characterized in that first the flake zinc powder of 5～25wt% and the flakey aluminium powder of 5～15wt% being stirred, add the inorganic additive of organic solvent, the dispersant of 1.1～1.8wt%, the corrosion inhibiter of 3～8wt% and the 3～10wt% of 25～40wt%, stirring 20～40min, makes base-material；
Add in base-material after the organic solvent of the modified resin of 5～15wt%, the organo silane coupling agent of 1～3wt% and 25～30wt% being stirred after probable, stir 30～50min, prepare chromium-free zinc aluminum anticorrosive paint；
Add in base-material after the organic solvent of the modified resin of 5～15wt%, the organo silane coupling agent of 1～3wt% and 25～30wt% being stirred after probable, stirring 30～50min, add the hydroxyethyl cellulose of 0.05～0.5wt%, stirring 20～50min, prepares chromium-free zinc aluminum anticorrosive paint.
2. the preparation method according to a kind of Chrome-free anticorrosive paint described in claim 1, it is characterised in that the piece footpath of described flake zinc powder is 10～15 μm, and thickness is 0.1～0.2 μm.
3. the preparation method according to a kind of Chrome-free anticorrosive paint described in claim 1, it is characterised in that the piece footpath of described flakey aluminium powder is 10～12 μm, and thickness is 0.1～0.2 μm.
4. the preparation method according to a kind of Chrome-free anticorrosive paint described in claim 1, organic solvent described in it is characterized in that is more than one in ethylene glycol ether acetate, butyl acetate, butyl methacrylate, dioctyl phthalate, acetone, cyclohexanone, MEK, isopropanol, n-butanol, ethylene glycol and propane diols, and more than one the organic solvent front and back adding twice is all identical.
5. the preparation method according to a kind of Chrome-free anticorrosive paint described in claim 1, it is characterised in that described dispersant is fatty alcohol polyethenoxy ether class.
6. the preparation method according to a kind of Chrome-free anticorrosive paint described in claim 1, it is characterised in that described corrosion inhibiter is thiocarbamide or is BTA.
7. according to the preparation method without a kind of Chrome-free anticorrosive paint described in claim 1, it is characterised in that described inorganic additive is for the nano silicon through nanoscale microemulsion surface modification or for through the nanometer silicon carbide of nanoscale microemulsion surface modification.
8. the preparation method according to a kind of Chrome-free anticorrosive paint described in claim 1, it is characterised in that described modified resin is more than one in epoxy modified acrylic resin, polyurethane modified epoxy and epoxy modified phenolic resin.
9. the preparation method according to a kind of Chrome-free anticorrosive paint described in claim 1, it is characterised in that described organo silane coupling agent is the one in organo silane coupling agent KH-550, organo silane coupling agent KH-560, organo silane coupling agent KH-570 and organo silane coupling agent KH-900.
10. the Chrome-free anticorrosive paint prepared by preparation method of a kind of Chrome-free anticorrosive paint as according to any one of claim 1～9.
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| CN106700669A (en) * | 2016-12-13 | 2017-05-24 | 天长市银狐漆业有限公司 | Cracking-preventing chromium-free bionic self-cleaning phosphate-based high-temperature anticorrosive coating and preparation method thereof |
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| CN106833034A (en) * | 2016-12-13 | 2017-06-13 | 天长市银狐漆业有限公司 | A kind of bionical automatically cleaning phosphate high-temperature anticorrosion paint of heat-resisting Chrome-free and preparation method thereof |
| CN107033636A (en) * | 2016-12-13 | 2017-08-11 | 天长市银狐漆业有限公司 | A kind of bionical automatically cleaning phosphate high-temperature anticorrosion paint of radiation proof Chrome-free and preparation method thereof |
| CN108425112A (en) * | 2018-05-28 | 2018-08-21 | 宁波沪荣汽车部件有限公司 | A kind of wear-resisting erosion resistance surface is modified the preparation process of galvanized steel plain sheet |
| CN109021776A (en) * | 2018-06-28 | 2018-12-18 | 江苏双汇电力发展股份有限公司 | A kind of aluminium coated steel pre-stranded wire end anticorrosion process |
| CN109504238A (en) * | 2018-11-23 | 2019-03-22 | 华南理工大学 | A kind of one-component self-curing chromium-free zinc aluminum anticorrosive paint and preparation and application |
| CN111548700A (en) * | 2020-04-26 | 2020-08-18 | 深圳亚太航空技术有限公司 | Novel chromium-free self-lubricating coloring aluminum coating for aviation and preparation method and application thereof |
| CN112480777A (en) * | 2020-12-04 | 2021-03-12 | 广东聚航新材料研究院有限公司 | Alcohol-soluble phenolic resin zinc-rich coating and preparation method thereof |
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2015
- 2015-04-05 CN CN201510157124.5A patent/CN106147564A/en active Pending
Cited By (11)
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| CN106700669A (en) * | 2016-12-13 | 2017-05-24 | 天长市银狐漆业有限公司 | Cracking-preventing chromium-free bionic self-cleaning phosphate-based high-temperature anticorrosive coating and preparation method thereof |
| CN106752138A (en) * | 2016-12-13 | 2017-05-31 | 天长市银狐漆业有限公司 | A kind of bionical automatically cleaning phosphate high-temperature anticorrosion paint of acid and alkali-resistance Chrome-free and preparation method thereof |
| CN106833034A (en) * | 2016-12-13 | 2017-06-13 | 天长市银狐漆业有限公司 | A kind of bionical automatically cleaning phosphate high-temperature anticorrosion paint of heat-resisting Chrome-free and preparation method thereof |
| CN107033636A (en) * | 2016-12-13 | 2017-08-11 | 天长市银狐漆业有限公司 | A kind of bionical automatically cleaning phosphate high-temperature anticorrosion paint of radiation proof Chrome-free and preparation method thereof |
| CN108425112A (en) * | 2018-05-28 | 2018-08-21 | 宁波沪荣汽车部件有限公司 | A kind of wear-resisting erosion resistance surface is modified the preparation process of galvanized steel plain sheet |
| CN109021776A (en) * | 2018-06-28 | 2018-12-18 | 江苏双汇电力发展股份有限公司 | A kind of aluminium coated steel pre-stranded wire end anticorrosion process |
| CN109504238A (en) * | 2018-11-23 | 2019-03-22 | 华南理工大学 | A kind of one-component self-curing chromium-free zinc aluminum anticorrosive paint and preparation and application |
| CN109504238B (en) * | 2018-11-23 | 2021-06-08 | 华南理工大学 | Single-component self-curing chromium-free zinc-aluminum anticorrosive paint and preparation and application thereof |
| CN111548700A (en) * | 2020-04-26 | 2020-08-18 | 深圳亚太航空技术有限公司 | Novel chromium-free self-lubricating coloring aluminum coating for aviation and preparation method and application thereof |
| CN112480777A (en) * | 2020-12-04 | 2021-03-12 | 广东聚航新材料研究院有限公司 | Alcohol-soluble phenolic resin zinc-rich coating and preparation method thereof |
| CN114989680A (en) * | 2022-06-13 | 2022-09-02 | 沈阳化工大学 | Environment-friendly, heat-insulating and corrosion-resistant water-based chromium-free zinc-aluminum coating and preparation method thereof |
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