CN101660154B - Non-phosphate film agent - Google Patents
Non-phosphate film agent Download PDFInfo
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- CN101660154B CN101660154B CN2009101835708A CN200910183570A CN101660154B CN 101660154 B CN101660154 B CN 101660154B CN 2009101835708 A CN2009101835708 A CN 2009101835708A CN 200910183570 A CN200910183570 A CN 200910183570A CN 101660154 B CN101660154 B CN 101660154B
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Abstract
The invention relates to a non-phosphate film agent, comprising the following components by weight percent: 2.5-4.5% of succinic acid, 0.8-2% of sodium molybdate, 0-3% of sodium nitrate, 0-5% of citric acid, 0-0.5% of sodium fluoride, 0-0.8% of tannin, 0-1.5% of oxalic acid, 0-0.05% of sodium dodecyl sulfate, the balance of water. The invention has the advantages that: the non-phosphate film agent contains no phosphor, thus being really environmentally friendly; antirust performance is good; combining power with molding powder and paint and adhesive force are all excellent, thus meeting ROHS standard; when in use, aluminum alloy work piece, galvanized work piece and steel work piece can be placed in the same bath solution for coating, thus greatly simplifying the production technology and reducing equipment investment; and suspended matter produced when being continuously used for three months is only 10-20 kilograms, thus solving the difficult problem that one day is stopped in production per week for clearing phosphated slag when using phosphoric film agent.
Description
Technical field
The present invention relates to a kind of non-phosphate film agent, it is used for the preceding operation of coating metal surfaces.
Background technology
Film agent is a kind of metal conditioner; can produce reaction with metal; when removing the metallic surface corrosion; form a kind of water insoluble, unreactiveness, firm attachment protective membrane in the metallic surface; this protective membrane helps preventing burning; also help in follow-up metallic surface spraying process, the engaging force of paint film, molding powder and the metal of spraying, sticking power are strengthened, thereby be widely used in the making industry of metal productss such as automobile, refrigerator, air-conditioning.
Film agent comprises phosphorous film agent and non-phosphate film agent two classes, and phosphorous film agent environmental pollution is serious, in use can produce a large amount of phosphatic waste water and waste residue, and the treatment process of these waste water and waste residue is comparatively complicated, and processing costs is also higher.Though there are some not phosphorous in the existing non-phosphate film agent, contain other objectionable constituent, as fluorine zirconic acid etc., these objectionable impuritiess also can pollute environment; Though also have some non-phosphate film agents not phosphorous, but its effect only is equivalent to rust-preventive agent, itself and metallic surface do not produce oxidation or replacement(metathesis)reaction, behind this non-phosphate film agent processing metal, the protective membrane that forms in the metallic surface can play certain effect that prevents burning, but the engaging force of this protective membrane and paint film and molding powder, sticking power are all very poor, and film of long duration is easy to peel off from the metallic surface; In addition, the non-phosphate film agent that has in use must be used deionized water, in case there is ion to enter production process, just must change medicament.
In addition, different types of film agent generally can only be at film on the dissimilar metal works on the market, for example: the general film agent that contains chromium that uses of Al alloy parts, iron and steel parts is then used phosphorous film agent more, and therefore different metal works can not be placed on when handling goes up film in the same tank liquor.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of non-phosphate film agent, and this non-phosphate film agent in use can be not incrust to the film that environment pollutes and generates.
The technical solution adopted in the present invention is: a kind of non-phosphate film agent, and its component and content are:
Succinic Acid 2.5---4.5%;
Sodium orthomolybdate 0.8---2%;
SODIUMNITRATE 0---3%;
Citric acid 0---5%;
Sodium Fluoride 0---0.5%;
Weibull 0---0.8%;
Oxalic acid 0---1.5%;
Sodium laurylsulfonate 0---0.05%;
Other are water, and all percentage ratios are weight percentage.
According to national regulation, phosphorus content is lower than 15% and promptly can be considered without phosphorus in the film agent.Therefore, all contain the phosphorus of certain composition in the existing non-phosphate film agent mostly, the present invention adopts Succinic Acid and Sodium orthomolybdate to realize basic last film function, and is not phosphorous fully, thoroughly solved the pollution of phosphorus to environment; And for the metal of unlike materials such as aluminium alloy, steel plate, Succinic Acid, Sodium orthomolybdate all can react film forming with it, and therefore different metal works can be placed on when handling goes up film in the same tank liquor; Sodium orthomolybdate can also make the film of generation produce different colors such as indigo plant, purple, gold according to the difference of temperature of reaction, acidity and the sheet metal that reacted, need not to be added with harmful heavy metals, can form firm colored oxide film with the metallic surface; The present invention can also adapt to various water quality.
As preferred version of the present invention, the content of SODIUMNITRATE is 0.2---3%.SODIUMNITRATE is an oxygenant, can improve the speed of film agent film on the metallic surface.
As another kind of preferred version of the present invention, the content of Sodium Fluoride is 0.01---0.5%.Sodium Fluoride can corroding metal, makes the metallic surface smooth, thereby therefore the easier film of going up also can play and improve the effect of going up film speed.
As another kind of preferred version of the present invention, the content of citric acid is 0.05---5%.Citric acid can be regulated the thickness of film.
As another kind of preferred version of the present invention, described non-phosphate film agent comprises the oxalic acid of 0.5---1.5% and/or the sodium laurylsulfonate of 0.01---0.05%, can adopt film on the spraying method during use.Can generate some iron ions when the aqueous solution of Succinic Acid and Sodium orthomolybdate and metal reaction in last membrane process, oxalic acid can chelated iron ion and is improved the acidity of film agent, the effect of film in the raising; In addition, the metallic surface often has some oil, ash, selects the sodium laurylsulfonate tensio-active agent for use, can get rid of these oil, ash well, makes to go up the smooth and even film layer of film.
As another kind of preferred version of the present invention, the content of Weibull is 0.02---0.8%.Weibull itself can generate rete with metal reaction and on its surface, but because the Weibull film formation time is longer, otherwise the rete that produces will be very thin, but therefore film on the adopting soaking method.Adopt Weibull to cooperate film on Succinic Acid and the Sodium orthomolybdate, can make the engaging force of film and metal better, and can guarantee that it can be too not thin.
When making film agent of the present invention, after each raw material dissolves in water and finishes, add a kind ofly down again, the sequencing that adds between the various raw materials is fixing, and temperature is that normal room temperature gets final product.
Use film in the present invention, temperature is 35 ℃--effect is better in the time of-55 ℃.
Advantage of the present invention has: described non-phosphate film agent is not phosphorous fully, real environmental protection; Rustless property is good; All reach good with engaging force, the sticking power of molding powder, paint, meet the ROHS standard.Al alloy parts, galvanized workpiece, iron and steel parts can be placed on during use and go up film in the same tank liquor, simplify production technique widely, reduce facility investment; Use the suspended substance that was produced in three months only to be the 10---20 kilogram continuously, solved and used phosphorous film agent to stop production weekly to remove the difficult problem of phosphatization slag in one day; Use the waste water flocculation agent post precipitation that the present invention produced, do not contain hazardous substance recycling or direct discharging.
Embodiment
Be further described with regard to specific embodiments of the invention below
Embodiment 1: Succinic Acid 4.5%, Sodium orthomolybdate 2.0%, all the other are water.
Embodiment 2: Succinic Acid 2.5%, Sodium orthomolybdate 0.8%, all the other are water.
Embodiment 1-2 all adopts Succinic Acid, Sodium orthomolybdate as main component, not phosphorous fully, can generate colour film on the sheet metal surface, whether the water during for film forming is that deionized water does not require, and the sheet metal of unlike materials such as Al alloy parts, galvanized workpiece, iron and steel parts can be placed in the same tank liquor, be film on the different sheet metal simultaneously.The time of the last film of embodiment 1-2 is 2-4 minute; To become protective membrane and molding powder, the engaging force of paint, sticking power be excellent.
Embodiment 3: Succinic Acid 4.5%, Sodium orthomolybdate 0.8%, SODIUMNITRATE 2.5%, all the other are water.
Embodiment 4: Succinic Acid 2.5%, Sodium orthomolybdate 2.0%, citric acid 5%, all the other are water.
Embodiment 5: Succinic Acid 3.5%, Sodium orthomolybdate 2.0%, Sodium Fluoride 0.5%, all the other are water.
Embodiment 6: Succinic Acid 3.5%, Sodium orthomolybdate 2.0%, SODIUMNITRATE 0.2%, citric acid 0.05%, Sodium Fluoride 0.01%, all the other are water.
Embodiment 3-6 has added at least a material in SODIUMNITRATE, citric acid or the Sodium Fluoride on the basis of Succinic Acid and Sodium orthomolybdate, the last film time is 1-2 minute, the engaging force of institute's film forming and molding powder, paint, sticking power are excellent, and rete is more even than embodiment 1-2 institute film forming.
Embodiment 7: Succinic Acid 4.5%, Sodium orthomolybdate 1.8%, SODIUMNITRATE 0.2%, citric acid 0.05%, Sodium Fluoride 0.01%, oxalic acid 0.5%, sodium laurylsulfonate 0.01%, all the other are water.
Embodiment 8: Succinic Acid 4.5%, Sodium orthomolybdate 1.8%, SODIUMNITRATE 0.2%, citric acid 0.05%, Sodium Fluoride 0.01%, oxalic acid 1.5%, sodium laurylsulfonate 0.05%, all the other are water.
Embodiment 7-8 compares with embodiment 6, last film better effects if: sodium laurylsulfonate can be got rid of oil, ash on the metallic surface as tensio-active agent, make and go up the smooth and even film layer of film, the last film time is 1-2 minute, and is shorter because of required time, can adopt film on the spraying method.
Embodiment 9: Succinic Acid 4.5%, Sodium orthomolybdate 1.8%, SODIUMNITRATE 0.2%, citric acid 0.05%, Sodium Fluoride 0.01%, Weibull 0.02%, all the other are water.
Embodiment 10: Succinic Acid 4.5%, Sodium orthomolybdate 1.8%, SODIUMNITRATE 0.2%, citric acid 0.05%, Sodium Fluoride 0.01%, Weibull 0.8%, all the other are water.
Embodiment 9-10 adopts Weibull to cooperate film on Succinic Acid and the Sodium orthomolybdate, can make the engaging force of film and metal better, and can guarantee that it can be too not thin.The last film time is about 5-10 minute, because of required time longer, but film on the adopting soaking method.
Embodiment 7-10 gained film agent in use, even contain ion in the water, non-phosphate film agent too can be successfully in metallic surface reaction film forming, the film and molding powder, the engaging force of paint, the sticking power that generate are excellent, meet Impact Test and 2 millimeters requirements of drawing the lattice test of 50 kilograms, and can in 3% neutral salt spray, reach 400---1000 hour by continuously tested.
Claims (6)
1. non-phosphate film agent is characterized in that: the described without phosphorus phosphorus that promptly do not contain fully, and its component and content are:
Succinic Acid 2.5---4.5%
Sodium orthomolybdate 0.8---2%
SODIUMNITRATE 0---3%
Citric acid 0---5%
Sodium Fluoride 0---0.5%
Weibull 0---0.8%
Oxalic acid 0---1.5%
Sodium laurylsulfonate 0---0.05%
Other are water, and all percentage ratios are weight percentage.
2. non-phosphate film agent according to claim 1 is characterized in that: the content of SODIUMNITRATE is 0.2---3%.
3. non-phosphate film agent according to claim 1 is characterized in that: the content of citric acid is 0.05---5%.
4. non-phosphate film agent according to claim 1 is characterized in that: the content of Sodium Fluoride is 0.01---0.5%.
5. according to claim 1 or 2 or 3 or 4 described non-phosphate film agents, it is characterized in that: the content of Weibull is 0.02---0.8%.
6. according to claim 1 or 2 or 3 or 4 described non-phosphate film agents, it is characterized in that: described non-phosphate film agent comprises the oxalic acid of 0.5---1.5% and/or the sodium laurylsulfonate of 0.01---0.05%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101835708A CN101660154B (en) | 2009-09-23 | 2009-09-23 | Non-phosphate film agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101835708A CN101660154B (en) | 2009-09-23 | 2009-09-23 | Non-phosphate film agent |
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| Publication Number | Publication Date |
|---|---|
| CN101660154A CN101660154A (en) | 2010-03-03 |
| CN101660154B true CN101660154B (en) | 2011-04-06 |
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| CN2009101835708A Expired - Fee Related CN101660154B (en) | 2009-09-23 | 2009-09-23 | Non-phosphate film agent |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103184446A (en) * | 2013-03-22 | 2013-07-03 | 常州大学 | Forming solution for environment-friendly non-phosphate ceramic film and preparation method and application thereof |
| EP3061847A4 (en) * | 2013-10-22 | 2017-07-26 | Henkel AG & Co. KGaA | Non-phosphorus chemical conversion treatment agent and treatment liquid for plastic working, chemical conversion coating, and metal material having chemical conversion coating |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102011114B (en) * | 2010-12-31 | 2012-06-20 | 沈阳帕卡濑精有限总公司 | Phosphorous ion-free treating agent for treating steel plate |
| CN105925971B (en) * | 2016-06-14 | 2018-02-27 | 中山市东升镇威尔特表面技术厂 | Environment-friendly type film agent |
| CN108728837A (en) * | 2017-04-20 | 2018-11-02 | 昆山汉鼎精密金属有限公司 | Non-phosphate film agent, non-phosphate film processing method and products thereof |
| CN107201513B (en) * | 2017-06-02 | 2019-03-19 | 山东大学 | A kind of pretreatment of metal surface liquid and its application based on the Phosphateless environmentally friendly that tannic acid is main film forming substance |
| CN107190253A (en) * | 2017-06-20 | 2017-09-22 | 合肥太通制冷科技有限公司 | A kind of plate pipe evaporator production technology |
| CN107267972A (en) * | 2017-06-20 | 2017-10-20 | 合肥太通制冷科技有限公司 | A kind of aluminium alloy epithelium reagent |
| CN114182244A (en) * | 2021-12-17 | 2022-03-15 | 惠州市四维化工有限公司 | Environment-friendly nanometer multifunctional coating agent |
-
2009
- 2009-09-23 CN CN2009101835708A patent/CN101660154B/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103184446A (en) * | 2013-03-22 | 2013-07-03 | 常州大学 | Forming solution for environment-friendly non-phosphate ceramic film and preparation method and application thereof |
| CN103184446B (en) * | 2013-03-22 | 2015-07-01 | 常州大学 | Forming solution for environment-friendly non-phosphate ceramic film and preparation method and application thereof |
| EP3061847A4 (en) * | 2013-10-22 | 2017-07-26 | Henkel AG & Co. KGaA | Non-phosphorus chemical conversion treatment agent and treatment liquid for plastic working, chemical conversion coating, and metal material having chemical conversion coating |
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| Publication number | Publication date |
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| CN101660154A (en) | 2010-03-03 |
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Address after: 211134 Tangshan Peak Industrial Park, Jiangning District, Nanjing, Jiangsu Patentee after: Nanjing Bo Ke Ke Biological Technology Co., Ltd. Address before: 210000 Nanjing, Jiangning, Jiangsu Province peak Industrial Park Long Chemical Industry Patentee before: Nanjing Jiujiu Chemical Technology Development Co., Ltd. |
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Granted publication date: 20110406 Termination date: 20190923 |