CN100441643C - Electrophoretic nano-coating - Google Patents
Electrophoretic nano-coating Download PDFInfo
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- CN100441643C CN100441643C CNB200510051844XA CN200510051844A CN100441643C CN 100441643 C CN100441643 C CN 100441643C CN B200510051844X A CNB200510051844X A CN B200510051844XA CN 200510051844 A CN200510051844 A CN 200510051844A CN 100441643 C CN100441643 C CN 100441643C
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
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- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The combination of employing electrophoretic technology with high covering power and the capability of using polymer nano-emulsion particles to produce a coherent layer of anti-corrosive polymer coating leads to the formation of coating layers with desirable properties such as being an extremely thin, transparent and coherent layer with uniform deposition on corners, edges and small holes, and showing suitable hardness, good corrosion protection and strong adherence to the underlying substrates. The technology can thus be applied to various industries for the purpose of decoration and corrosion protection of conductive substrates.
Description
Technical field
The present invention relates to deposited polymer coating on the made electric conductivity base material of for example iron or other metal and alloy thereof such as aluminum magnesium alloy; be formed for the corrosionproof protection and the decoration of ornament layer, metal frame and the furniture of toy industry, and the protection of costume jewelry and metal picture frame.
Background of invention
Be used to realize that the traditional technology of anti-corrosion of metal protection often adopts organic polymer coating, as coating and lacquer.Electrophoresis process can have been produced the outstanding organic coating with ideal operation performance, and adopted by various industries as widely used technology and to surpass 30 years, for example be used for the coating of Agricultural equipment, utensil, automobile, auto parts, ship components, metal office equipment, lawn and garden equipment, furniture and other Industrial Metal main body.It has obtained noticeable development, the annual new purposes of all developing electrophoretic painting.
Because in recent years about the continuous increase of environment protection and publilc health and awareness of safety, in the surface finishing industry, developed numerous systems and replaced system based on organic solvent based on water.Yet, usually poor than coating quality based on the system of organic solvent based on the coating quality of the system of water.Kai Fa nanometer polymer emulsion makes a breakthrough in this field in recent years, and it has improved coating quality and has had perfect performance, has produced promising market potential, is particularly executing the building coating industry that relevant organic solvent debases the standard.For example, China and Hong Kong have been formulated planning chart and have been controlled at distributing of organic vapo(u)r in the Industrial processes.
Polymer emulsion in the electrophoretic painting for commercial applications for many years.Existing a lot of patent has been described the application of polymer emulsion in the electrophoretic painting process.Yet particle size of emulsion usually is covert, even be disclosed, also outside nano-scale range (the highest 100nm) or comprised that a major part surpasses the relative broad range of nano-scale usually.For example, the emulsion particle diameter of describing in people's such as Graun U.S. Pat 4,608,139 (on August 26th, 1986) is 40-1000nm, preferred 150-600nm, so median size is outside nanometer range.In people's such as Abbey U.S. Pat 4,511,446 (on April 16th, 1985), when allowing described particle diameter to be low to moderate 30nm, the median size of emulsion is not exclusively less than 100nm.Do not wish that another feature that employed emulsion has is to use the organic cosolvent that causes environment and safety problem in a large number.For example, February in 1993 people such as disclosed Chung on the 9th U.S. Pat 5,185,065, April in 1985 people such as disclosed Abbey on the 16th the U.S. Pat 4 of U.S. Pat disclosed Dudley on the 23rd January in 4,511,446,1979,136,074 and 1976 on August 31, people such as disclosed Kolish U.S. Pat 3,978,015 in emulsion always contain alcohol or other organic cosolvent and tensio-active agent.
Summary of the invention
The nanoparticle of nanoemulsions of the present invention has the very narrow size distribution between 10-100nm, and the use of organic cosolvent greatly reduces, usually less than about 1%.These nanoemulsions are except environmentally friendly; the coating of making by their since between the sedimentary nanoparticle of institute suitable interaction also demonstrate the performance of improvement, to prepare much thin, transparent non-porous, as to have outstanding corrosionproof protection coating that reaches.When nanoemulsions uses as binding agent in the electrophoretic painting process because the granularity of nanoparticle is little, can produce have outstanding stability, low-permeability, good impregnability and mobile coating.This allows them to penetrate in surperficial superfine hole, breach and the hollow billet shape zone of metal object.This has special advantage when applying very complicated shape so that high-quality uniform coating is provided.Film or the formation with ultrathin membrane of several nano thickness (several microns of for example about 10-) produce the highly transparent layer that one deck can not intuitively be perceived by contact or naked eyes.Thereby they are particularly suitable for decorating costume jewelry.In the codeposition process with other pigment particle, nano_scale particle can penetrate in the gap of big particulate.Thereby the hardness, coherency, slickness and the brightness that contain the coating of pigment can greatly improve.The use of nanoemulsions can reduce the generation of pigment electrophoretic separation, reduces fissured formation, and can produce the rainbow coating with high potentiality with the development of adaptation future market according to customer requirement.
Electrophoretic nano-coating technology of the present invention is that polymer nanocomposite emulsion or the nanoemulsions that contains pigment combine with electrophoresis process.The application that is used for the polymer emulsion with nano level particle size range of electrophoretic painting is emerging.Use the good throwing power of electrophoresis process can produce ideal coating with the combination of the polymer nanocomposite emulsion that deposits non-porous, fine and close polymer nanocomposite coating.This has enlarged the application of polymer nanocomposite emulsion on functional and decorative coating.At first, it has opened up new Application Areas, as for light metal and alloy thereof the protectiveness clad can coating of aluminum magnesium alloy for example.Secondly, the deposition of the ornament layer that forms according to customer requirement will be extended its application in the toy industry, extend for the corrosionproof protection of metal frame and furniture and decoration and for the application of protecting costume jewelry and metal picture frame.
In the electrophoretic nano emulsion of conductive substrate immersion, make electric current through metal base and emulsion based on water.Charged nanoparticle, and sticks to substrate surface and forms electric insulation coating layer because electric field action and moving towards base material together with the paint particles of other existence.This coating has covered whole metal base, and can regulate the electric current process system of insulation layer to prevent to apply subsequently of formation automatically, even also can form coating very uniformly at the recessed region of complicated shape product.After base material is coated, can in baking oven, solidify so that the nanometer polymer particulate flows and is cross-linked with each other.For a lot of industrial application, this provides good protection of ideal and decorate properties for the coating that forms.
Detailed Description Of The Invention
Nanoemulsions of the present invention is to contain to be up to 100nm, the preferred polymer emulsion based on water of the nanometer particle size particulate between 10-100nm.Emulsion generally contains the emulsification particulate of the polymkeric substance of water dispersible vinylformic acid or modified acroleic acid, however the polymkeric substance of other water-dispersion for example urethane also can use.Now, many solids contents are commercially available at the polymer emulsion of about 40-60%.Can confirm that the emulsion of the nano-scale range declared is a nanoemulsions by atomic force microscope or transition electron microscope.
Nanoemulsions contains the emulsification nano level particle diameter particulate of water and ionic polymer, and other electrophoresis additive commonly used.These additives comprise emulsifying agent, defoamer, levelling agent, siccative, thickening material, thixotropic agent, weighting agent, sanitas and analogue.All these additives are commercially available.For example, the T-731 dispersion agent and TT-935 thickening material, 5040 dispersion agents of Henkel company and EFKA 3580 levelling agents and the defoamer 2526 of NXZ defoamer and EFKA Additives that provide of Rohm and Hass company.Basically should not contain organic solvent (promptly less than about 1%).
When the needs Clear coating, preparation does not contain the nanoemulsions of pigment.At first, water, preferred distilled water dilute commercially available polymer nanocomposite emulsion, and the solids content of regulating emulsion is to suitable settling concentration.This can be about 10-20%, also can use other concentration if desired.In order to obtain satisfactory coating in electrophoresis process, electrical conductivity of water must be controlled at and be lower than 5 μ S/cm.This can assign to realize by the one-tenth of suitable selection emulsion.Equally, the pH value of emulsion is adjusted to alkalescence with the electric charge of controlling polymers particulate and regulate deposition process.Preferably, pH value scope is at 7.8-9.0, and this can be by adding suitable alkali in emulsion, for example 2-amino-2-methyl-1-propanol (AMP-95), N, and N-dimethylethanolamine or triethylamine are realized.In order to obtain high-quality coating, have the emulsion of suitable solids concn, specific conductivity and pH must be before use stirring by for example time expand come ageing (reaching balance).Digestion time, temperature and stir speed (S.S.) influence each other, and increase one of them and can allow the bigger range of choice of other parameter.Suitable ageing program can be included in the speed of changeing with per minute 1500 under the envrionment conditions and stir at least 48 hours in the groove that the PP plate is made.
Can use the electrophoretic coating program of standard in the present invention.Typically, in the ultrasonic bath that is containing sanitising agent under 30 ℃ of constant temperature with the conductive substrate degreasing of precoating 20 minutes.Then holding before tool is immersed in aged nanoemulsions, with tap water and pure water rinsing base material with suitable.By the stirring under the room temperature, between conductive substrate and electrode relative with it, for example iron, apply the driving voltage of 15-30V, and continue about 15-60 second.After from electrophoresis chamber, taking out, for example the base material that applies with pure water rinsing then with the tap water flushing respectively at least two minutes to remove any uncoated emulsion.Before putting into baking oven baking, the workpiece after the flushing for example air drying at least 10 minutes, there is not tangible water on the surface.With workpiece under about 100-180 ℃ constant temperature the about 20-30 of processing treatment minute.Obtain optically transparent coating.The film that obtains is like this formed and is not contained pigment particle by the straight polymer coating.
Perhaps, can adopt from nano-emulsion bath of liquid galvanic deposit to obtain containing the nano-complex coating of pigment.In this case, the galvanic deposit pigment particle deposits in electrophoresis process simultaneously with nanoparticle.Because the emulsion particle of nano-scale combines with the strong of pigment particle, the nano-complex coating has good corrosionproof protection and demonstrates other perfect performance.
The typical method for preparing the nano-emulsion bath of liquid that contains pigment is as follows:
(1) prescription as requested will for example add in the container in an amount of pure water of weight part, dispersion agent, defoamer, sanitas and levelling agent and some pH regulator agent, and use dispersion machine thorough mixing under high stirring velocity.
(2) the commercially available nanoemulsions that will contain half content of desired nanoparticle joins in the container and thorough mixing.
(3) join in the container a selected amount of pigment and weighting agent and thorough mixing.
(4) mixture that will obtain is like this transferred to grinding machine for grinding.
(5) will transfer in the container by the slurry that grinding obtains, add the nanoemulsions of residual content then.
(6) siccative, thickening material and pH regulator agent are added in the container with above-mentioned slurry thorough mixing.
(7) last, by in slurry, adding pure water and pH regulator agent adjusting solids content and pH value, obtain containing the nano-emulsion bath of liquid of pigment respectively to 10-20% and 7.8-9.0.
This nano-emulsion bath of liquid contains pigment and additive.Pigment in this nanoemulsions can be generally to be used for electrophoretic any colored compound in coatings industry, iron oxide black that is used for coating and carbon black that for example those are commercially available.The preferable range of pigment is about 1-30wt% in the emulsion.The preferred 2-amino-2-methyl-1-propanol of pH regulator agent (AMP-95).The specific conductivity of pure water preferably is controlled at and is lower than 5 μ S/cm.Provide the representative formula of nano-emulsion bath of liquid below:
The composition weight percent, %
Nanoemulsions 50-80
Pigment and weighting agent 1-30
Dispersion agent 0.1-0.5
Thickening material 0.2-5
Siccative 1-4
PH regulator agent 0.1-0.5
Defoamer 0.01-0.05
Pure water 5-10
Workpiece, typically is applied to coating on the conductive substrate in containing the nano-emulsion bath of liquid of pigment after 20 minutes in grease removal under 30 ℃ the constant temperature in containing the ultrasonic bath of sanitising agent.In order to utilize electrophoresis process to produce compound coating,, conductive substrate is immersed in the electrophoresis chamber, in for example polyacrylic moisture nanoemulsions using under the driving voltage.After base material is coated, from the PP groove, take out, washed respectively at least two minutes by pure water then by tap water.Before putting into baking oven baking, the workpiece after the flushing air drying at least 10 minutes, there is not tangible water on the surface of workpiece.The nano-composite coating that obtains can be used as undercoat or clad can coating.The typical operation scope of the working parameter of electrophoresis and bake process is compiled in table 1.
Table 1
In order further to illustrate the present invention, list various unrestriced embodiment below.
The polymer nanocomposite coating that embodiment 1-is transparent
Obtain the acrylate copolymer nanoemulsions that trade mark is ZBE 612 from Tsingdao Ocean Chemical Institute.The average polymer particle diameter of this nanoemulsions is about 50nm.Provide as it, solids content and pH value are respectively 40.2% and 7.8.Two parts of pure water and a nanoemulsions are mixed in the electrophoresis chamber that the PP plate is made.By adding alkali the pH value of nanoemulsions is adjusted to 8.2 ± 0.3.By under envrionment conditions, stirring resulting emulsion 48 hours and slaking.On multiple electroconductibility workpiece (steel, iron, copper and aluminum magnesium alloy thereof), carry out electrophoresis process then.At last, behind the baking workpiece, obtain transparent polymer nanocomposite coating.Use this emulsion to produce the working parameter of optimization of transparent nano coating and the performance of resulting coating is listed in the table 2.
Table 2. working parameter and performance
Embodiment 2-black composite Nano undercoat
Obtaining median size from Tsingdao Ocean Chemical Institute is that 50nm, label are the nanoemulsions of ZBE611.The composite Nano emulsion A and the B that contain pigment according to two kinds of the formulation that provides in the table 3.Utilize A and B composite Nano emulsion to realize the cataphoretic coating of multiple electroconductibility workpiece (steel, iron, copper and aluminum magnesium alloy thereof) respectively.Behind the baking workpiece, obtain the composite Nano coating of black.The operating restraint and the Performance Evaluation that apply the optimization of program in table 4, have been listed.
The composition of the composite Nano emulsion of table 3.A and B
The operating restraint and the performance thereof of the optimization of table 4. black composite Nano coating
The ornamental nano coating of embodiment 3-golden
With label is that the acrylate copolymer nanoemulsions of ZBE 612 and golden thickener that concentration is 55-65ml/L mix in the groove that the PP plate is made.Obtain the golden nanoemulsions by stirring after golden slurry fully disperseed.Average polymer particle diameter in ZBE 612 nanoemulsions is about 50nm.Provide as it, the solids content of nanoemulsions and pH value are respectively 40.2% and 7.8.Two parts of pure water and a golden nanoemulsions are mixed in electrophoresis chamber.The pH value of nanoemulsions is adjusted to 8.2 ± 0.3.Stirred 48 hours and ageing by the golden nanoemulsions that under envrionment conditions, will dilute.Use multiple electroconductibility workpiece (steel, iron, copper and aluminum magnesium alloy thereof) to carry out electrophoresis process then.At last, behind the baking workpiece, obtain golden polymer nanocomposite coating.The working parameter of this emulsion optimization and the production operation scope of golden nano coating in table 5, have been listed.
The working parameter and the performance thereof of the optimization that the golden nano coating of table 5. is produced
Under the prerequisite that does not break away from essence of the present invention and scope, can make various changes and correction to the inventive method and product.Various specific embodiments described herein is intended to further illustrate the present invention, but not limits it.
Claims (10)
1. electrophoretic coating method, wherein the electric conductivity base material contacts with the electrophoretic coating bath composition, and apply electric current thereon, its improvement comprises that application composition is the equilibrated water-base emulsion of ionic polymer particles of the conductivity of pH value with 7.8-9,800-1500 μ S/cm, and the median size of wherein said ionic polymer particles is 10-100nm.
2. according to the process of claim 1 wherein that applying bath composition has the pH value of 7.9-8.5 and the specific conductivity of 800-1300 μ S/cm.
3. but apply the pigment that bath composition does not contain electrophoretic coating according to the process of claim 1 wherein.
4. but apply the pigment that bath composition contains electrophoretic coating according to the process of claim 1 wherein.
5. apply the solid that bath composition contains the 1-30 weight percent according to the process of claim 1 wherein.
6. according to the process of claim 1 wherein that applying is to carry out 15-60 by the driving voltage that at room temperature uses the 10-30 volt to realize second.
7. according to the process of claim 1 wherein the formed coating of baking.
8. according to the method for claim 7, wherein toast under 100-180 ℃ of temperature and carried out 20-30 minute.
9. according to the method for claim 7, but wherein apply the pigment that bath composition does not contain electrophoretic coating.
10. according to the method for claim 7, but wherein apply the pigment that bath composition contains electrophoretic coating.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/772,313 US20050173248A1 (en) | 2004-02-06 | 2004-02-06 | Electrophoretic nano-coating |
| US10/772313 | 2004-02-06 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1654558A CN1654558A (en) | 2005-08-17 |
| CN100441643C true CN100441643C (en) | 2008-12-10 |
Family
ID=34826578
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200510051844XA Active CN100441643C (en) | 2004-02-06 | 2005-02-05 | Electrophoretic nano-coating |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US20050173248A1 (en) |
| CN (1) | CN100441643C (en) |
| HK (1) | HK1081578A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010119443A1 (en) * | 2009-04-13 | 2010-10-21 | Yissum Research Development Company Of The Hebrew University Of Jerusalem, Ltd. | Process for electrochemical coating of conductive surfaces by organic nanoparticles |
| US8681417B2 (en) * | 2011-12-27 | 2014-03-25 | Visitret Displays Ou | Fast response electrophoretic display device |
| JP6415594B2 (en) * | 2013-12-20 | 2018-10-31 | ビーエイエスエフ・コーティングス・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツングＢＡＳＦ Ｃｏａｔｉｎｇｓ ＧｍｂＨ | Method for producing pigment and filler-containing preparation |
| US20200115565A1 (en) * | 2017-04-11 | 2020-04-16 | Hewlett-Packard Development Company, L.P. | Polymer coating of metal alloy substrates |
| CN115101891B (en) * | 2022-07-19 | 2024-03-05 | 中材锂膜有限公司 | Preparation method of lithium ion battery diaphragm |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4608139A (en) * | 1985-06-21 | 1986-08-26 | Scm Corporation | Electrocoating process using shear stable cationic latex |
| CN1176318A (en) * | 1996-08-26 | 1998-03-18 | 佳能株式会社 | Electrodeposition coated member and electrodeposition coating material |
| CN1378567A (en) * | 1999-10-20 | 2002-11-06 | 巴斯福股份公司 | Method for producing aqueous dispersion of particles that are made up of polymers and inorganic solid matter which consists of fine particles |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3978015A (en) * | 1971-04-05 | 1976-08-31 | Mobil Oil Corporation | Three component electrodeposition system |
| US4136074A (en) * | 1972-12-29 | 1979-01-23 | Canada Wire & Cable Limited | Process and bath composition for increasing the rate of polymer deposition in electrocoating |
| FR2476484A1 (en) * | 1980-02-22 | 1981-08-28 | Elf Aquitaine | COMPOSITIONS FOR THE MOISTURIZATION OF KERATINIC SUBSTANCES CONSISTING OF ALPHA AMINO ACID SULFOXIDES |
| US4511446A (en) * | 1983-07-14 | 1985-04-16 | Scm Corporation | Cathodic electrocoating composition compounded with latex binder for enhanced gloss retention |
| US5185065A (en) * | 1991-08-01 | 1993-02-09 | E. I. Du Pont De Nemours And Company | Low temperature coring cathodic electrocoating composition |
| FR2740340B1 (en) * | 1995-10-30 | 1997-12-05 | Oreal | USE OF CARBOXYLIC ACIDS CARRYING A SULFURED FUNCTION TO PROMOTE SKIN DEQUAMATION OR STIMULATE EPIDERMAL RENEWAL |
| US5672432A (en) * | 1995-11-16 | 1997-09-30 | Basf Corportion | Cathodic electrocoat compositions containing self-crosslinking polymers |
| US5667894A (en) * | 1996-06-05 | 1997-09-16 | E. I. Du Pont De Nemours And Company | Cathodic electrocoating compositions containing methane sulfonic acid as a neutralizing agent |
| US5744531A (en) * | 1996-06-24 | 1998-04-28 | Ppg Industries, Inc. | Anionic electrocoating compositions containing hydroxyalkylamide curing agents |
| US6214188B1 (en) * | 1998-12-21 | 2001-04-10 | Basf Corporation | Anodic electrocoat having a carbamate functional resin |
| US6132581A (en) * | 1999-04-22 | 2000-10-17 | Ppg Industries Ohio, Inc. | Electrocoating compositions containing polyvinylpyrrolidone crater control agents |
| US6342144B1 (en) * | 1999-12-15 | 2002-01-29 | Basf Aktiengesellschaft | Cured multilayer coating and processing for its production |
| US6376616B1 (en) * | 1999-12-20 | 2002-04-23 | Basf Corporation | Pigment dispersants having anionic functionality for use in anodic electrocoat compositions |
| JP4060620B2 (en) * | 2002-03-26 | 2008-03-12 | 日本ペイント株式会社 | Electrodeposition coating method using lead-free cationic electrodeposition paint |
-
2004
- 2004-02-06 US US10/772,313 patent/US20050173248A1/en not_active Abandoned
-
2005
- 2005-02-05 CN CNB200510051844XA patent/CN100441643C/en active Active
-
2006
- 2006-02-10 HK HK06101800.2A patent/HK1081578A1/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4608139A (en) * | 1985-06-21 | 1986-08-26 | Scm Corporation | Electrocoating process using shear stable cationic latex |
| CN1176318A (en) * | 1996-08-26 | 1998-03-18 | 佳能株式会社 | Electrodeposition coated member and electrodeposition coating material |
| CN1378567A (en) * | 1999-10-20 | 2002-11-06 | 巴斯福股份公司 | Method for producing aqueous dispersion of particles that are made up of polymers and inorganic solid matter which consists of fine particles |
Also Published As
| Publication number | Publication date |
|---|---|
| US20050173248A1 (en) | 2005-08-11 |
| HK1081578A1 (en) | 2006-05-19 |
| CN1654558A (en) | 2005-08-17 |
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