CN107955467B - Self-deposition coating based on PVDC resin as main material and preparation method and application thereof - Google Patents
Self-deposition coating based on PVDC resin as main material and preparation method and application thereof Download PDFInfo
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- CN107955467B CN107955467B CN201711180123.8A CN201711180123A CN107955467B CN 107955467 B CN107955467 B CN 107955467B CN 201711180123 A CN201711180123 A CN 201711180123A CN 107955467 B CN107955467 B CN 107955467B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/04—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C09D127/08—Homopolymers or copolymers of vinylidene chloride
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
- B05D7/142—Auto-deposited coatings, i.e. autophoretic coatings
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention discloses an autodeposition coating based on PVDC resin as a main material, and a preparation method and application thereof, and belongs to the technical field of metal coating. The paint is prepared from PVDC resin, SBR resin, water-based wax, an emulsifier, a film-forming auxiliary agent, a flatting agent, a wetting agent, a dispersing agent, color paste and a defoaming agent. The degreased and pickled steel substrate workpiece is immersed in the self-deposition working solution to react to form a uniform resin coating, the coating has certain water washing resistance and wet film adhesion, and after washing and drying, the resin coating has the corrosion resistance equivalent to that of a common electrophoretic primer. The method has the advantages of simple process, no need of phosphating treatment, no passivation of heavy metal ions, no reaction washing, low treatment temperature, low cost and short construction production line.
Description
Technical Field
The invention belongs to the technical field of metal surface treatment and metal coating, and particularly relates to an autodeposition coating based on PVDC resin as a main material, and a preparation method and application thereof.
Background
The self-deposition coating is a full-immersion water-based coating which can automatically cover the surface of a steel substrate by only chemical reaction without electrifying. The coating has the remarkable characteristic that the performance of a coating film directly deposited on the surface of a steel substrate can be close to that of a cathode electrophoretic coating without phosphating pretreatment. The self-deposition coating is composed of resin, pigment, oxidant, acid and water, and the emulsion particles in the self-deposition coating in the solution are demulsified and attached to the steel part by the chemical action of a micro battery formed by the steel substrate in an acidic solution, and a wet film with hydrophobic property is formed, and the wet film can resist washing with water under certain pressure without falling off, and a continuous corrosion-resistant resin coating with certain thickness is formed after baking.
From the 70 s to the 80 s of the last century, a great deal of research on autodeposition coatings and autodeposition processes thereof has been carried out by a great number of experts and scholars in the world, and great progress has been made, and a great number of patent technologies have been invented successively. Countries such as the united states, europe, and japan have established a certain number of autodeposition coating lines in succession. However, the rising of the thick-film cathode electrophoretic paint caused the self-electrophoretic paint to be in a state of stagnation at the end of the 80 th century, and some established production lines were gradually replaced by phosphating pretreatment and cathode electrophoresis. In the later 90 s of the last century, the coating development mode of low cost, environmental protection and pollution-free is adopted, and experts and scholars are prompted to research the self-deposition coating and the self-deposition process again. In recent years, a large number of patents and literature on autodeposition coatings and autodeposition processes have emerged, and the properties of autodeposition coatings reported in the patents and literature have been greatly improved over previous and again have a range of applications. However, the development of this technique is hampered by the disadvantages that, among others, the use of ultrafiltration techniques for closed-loop washing is not possible, which leads to a high loss of liquid from the autodeposited coating and, in order to achieve higher performance, the wet film is subjected to reactive washing after the autodeposited coating. In order to ensure the stability of the reaction water washing tank liquid, the pollution degree of the reaction water washing after the self-deposition coating needs to be monitored, once the upper limit of the conductivity is reached, overflow discharge is needed, the pressure of sewage treatment is caused, and the operation process is increased by the reaction water washing. In addition, the general wet film needs to be baked in two stages, wherein the temperature of the first stage is 70 ℃, and the temperature of the second stage is 120 ℃.
Disclosure of Invention
Therefore, aiming at the defects that the existing autodeposition coating needs reaction washing to improve the performance, and the washing after autodeposition is required to overflow regularly to ensure the bath solution quality of the reaction washing, which brings larger sewage treatment pressure, and the drying wet film is sectional type drying, and the drying temperature is higher, the PVDC type autodeposition coating which does not need reaction washing and is dried at a low temperature and a single section, and the preparation method and the application thereof are provided.
The technical scheme adopted by the invention is as follows: the self-deposition coating based on the PVDC resin as the main material is prepared from the PVDC resin, SBR resin, water-based wax, an emulsifier, a film-forming assistant, a leveling agent, a wetting agent, a dispersing agent, color paste and a defoaming agent.
The self-deposition coating based on PVDC resin as a main material comprises the following components in percentage by weight:
the PVDC resin can be PVDC resin emulsion, the solid content of the resin emulsion is 30-70 wt%, and the resin emulsion is acidic or can stably exist under the acidic system condition.
The SBR resin can be SBR resin emulsion, the solid content of the resin emulsion is 20-60 wt%, and the resin emulsion is acidic or can stably exist under the acidic system condition.
The aqueous wax can be aqueous wax emulsion, the solid content of the aqueous wax emulsion is 10-50 wt%, and the emulsion is acidic or can stably exist under the acidic system condition.
The emulsifier is selected from nonionic or anionic surfactant, such as fatty alcohol polyoxyethylene ether, isomeric tridecanol polyoxyethylene ether, sodium alkylsulfonate, sodium alkylbenzenesulfonate, sodium dodecyl sulfate, and alkylphenol polyoxyethylene ether (OP-10).
The film-forming assistant is one or a mixture of more than two of propylene glycol methyl ether, propylene glycol phenyl ether, benzyl alcohol, dodecyl alcohol ester and ethylene glycol butyl ether.
The levelling agent, wetting agent, dispersant and defoamer are all from commercially available auxiliaries, which are directly available, meet the requirements for stable presence under acidic conditions, and are from products of digao, bike and modenhames.
A preparation method of an autodeposition coating based on PVDC resin as a main material comprises the following steps: adding an emulsifier into water under medium-low speed stirring, uniformly stirring, then adding a film-forming auxiliary agent, a flatting agent, a wetting agent, a dispersing agent and a defoaming agent under medium-low speed stirring, uniformly stirring, then adding PVDC resin, SBR resin, water-based wax and color paste under medium-high speed stirring, and uniformly stirring.
The emulsifier is stirred at a medium and low speed in the stirring and dissolving process, the emulsifier is preferably dispersed and dissolved, the stirring is not suitable for too fast, if the foaming is too large in the stirring process of the several auxiliaries, the defoaming agent can be partially or completely added in advance to control the foaming without the feeding sequence, after all the materials are added and stirred uniformly, the materials are discharged and filtered, larger particles are removed, and the solid content of the discharged product is 20-40 wt%. The medium-low speed stirring is carried out at 50-200 r/min; the medium-speed stirring is at 200-; the medium-high speed stirring is carried out at the speed of 800-2000 r/min.
The self-deposition coating based on PVDC resin as a main material is applied to the coating of a steel substrate workpiece. The method comprises the following steps:
1) pretreatment: sequentially degreasing, washing, pickling and washing with pure water for the steel substrate workpiece;
2) and (3) self-deposition: adding 4-6wt% of the self-deposition coating based on PVDC resin as a main material, 3-10wt% of a cylinder opener and the balance of pure water into an acid-resistant and fluorine-resistant reaction tank with a temperature control and mechanical stirrer according to weight percentage, wherein the acid-resistant and fluorine-resistant reaction tank is obtained from a deposition working solution; immersing the pretreated steel substrate workpiece into an autodeposition working solution, setting the temperature to be 20 +/-2 ℃, and setting the autodeposition time to be as follows: 2.5-3 min;
3) taking out the steel substrate workpiece after the self-deposition, drying the steel substrate workpiece at the single-stage low temperature of 75-85 ℃, cooling the steel substrate workpiece to room temperature, and directly obtaining a layer of coating film on the steel substrate workpiece without reaction and water washing.
Compared with the prior art, the self-deposition coating provided by the invention has the following advantages:
1. the self-deposition coating disclosed by the invention is a product which can achieve higher performance without reaction washing, does not need reaction washing, has low requirement on the overflow amount of washing after self-deposition, and reduces the sewage treatment burden.
2. The self-deposition coating is a preferable resin and auxiliary agent suitable for low-temperature film forming, and a product is dried at a low temperature in a single section, so that energy sources and a drying field are saved.
3. The self-deposition coating can be used as a single component, and can also be divided into two parts of emulsion and color paste during production, wherein the storage stability of the product divided into the emulsion and the color paste is greatly improved.
4. The self-deposition coating is particularly suitable for coating metal parts, replaces the phosphating pretreatment and is matched with the coating process of cathode electrophoresis, and directly performs self-deposition coating after degreasing and acid pickling to form a continuous self-deposition coating which has good corrosion resistance after being cured;
5. the autodeposition coating is adopted for autodeposition, the problem of poor coating of an inner cavity and an inner surface is solved, and the part which can be immersed into the autodeposition working solution can be coated indiscriminately;
6. the self-deposition coating has the advantages of low product cost, simple construction process, simplified flow, energy conservation and environmental protection.
7. Washing with water without reaction. After the autodeposition coating is finished, the autodeposition coating enters a reaction washing stage after being washed by water to carry out a supplementary reaction so as to achieve higher performance requirements, which has high requirements on the washing conductivity after the autodeposition reaction, but the autodeposition cannot use an ultrafiltration technology, closed-loop washing cannot be realized, and washing water needs to be periodically overflowed and discharged, so that the environmental protection pressure is caused.
8. The low-temperature baking is carried out, compared with the baking requirements of other products, the baking temperature is about 120 ℃, the baking temperature of the invention is 75-85 ℃, the self-drying curing can be carried out even under the condition of enough storage sites for 2 weeks, and the salt spray test reaches 700 hours.
9. The degreased and pickled steel substrate workpiece is immersed in the self-deposition working solution to react to form a uniform resin coating, the coating has certain water washing resistance and wet film adhesion, and after washing and drying, the resin coating has the corrosion resistance equivalent to that of a common electrophoretic primer. Has the advantages of simple process, no need of phosphating treatment, no passivation of heavy metal ions, no reaction washing, low treatment temperature, low cost and short construction production line
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The specific experimental procedures or conditions not specified in the examples were performed according to the procedures or conditions of the conventional experimental procedures described in the literature in the field. The reagents or apparatus used are not indicated by the manufacturer, and are all conventional reagents which are commercially available.
Example 1
The self-deposition coating comprises the following substances in percentage by mass:
(II) the preparation method comprises the following steps: weighing 80% of deionized water by weight, adding isomeric tridecanol polyoxyethylene ether into water under the condition of low-speed stirring at 200r/min, uniformly stirring, adding dodecyl alcohol ester, a flatting agent, a wetting agent, a dispersing agent and a defoaming agent under the condition of medium-speed stirring at 500r/min, uniformly stirring, adding PVDC resin, SBR resin, water-based wax and color paste under the condition of medium-speed stirring at 1000r/min, uniformly stirring, adding the rest 20% of deionized water, uniformly stirring, discharging, filtering and removing larger particles.
Example 2
The self-deposition coating comprises the following substances in percentage by mass:
(II) the preparation method comprises the following steps: weighing 80% of deionized water by weight, adding isomeric tridecanol polyoxyethylene ether into water under the condition of low-speed stirring at 200r/min, uniformly stirring, adding dodecyl alcohol ester, a flatting agent, a wetting agent, a dispersing agent and a defoaming agent under the condition of medium-speed stirring at 500r/min, uniformly stirring, adding PVDC resin, SBR resin, water-based wax and color paste under the condition of medium-speed stirring at 1000r/min, uniformly stirring, adding the rest 20% of deionized water, uniformly stirring, discharging, filtering and removing larger particles.
Example 3
The self-deposition coating comprises the following substances in percentage by mass:
(II) the preparation method comprises the following steps: weighing 80% of deionized water by weight, adding sodium dodecyl sulfate into water under low-speed stirring at 200r/min, uniformly stirring, adding propylene glycol methyl ether, a flatting agent, a wetting agent, a dispersing agent and a defoaming agent under medium-speed stirring at 500r/min, uniformly stirring, adding PVDC resin, SBR resin, water-based wax and color paste under high-speed stirring at 1000r/min, uniformly stirring, adding the remaining 20% of deionized water, uniformly stirring, discharging, filtering and removing larger particles.
Example 4
The self-deposition coating comprises the following substances in percentage by mass:
(II) the preparation method comprises the following steps: weighing 80% of deionized water by weight, adding sodium dodecyl sulfate into water under low-speed stirring at 200r/min, uniformly stirring, adding propylene glycol phenyl ether, a flatting agent, a wetting agent, a dispersing agent and a defoaming agent under medium-speed stirring at 500r/min, uniformly stirring, adding PVDC resin, SBR resin, water-based wax and color paste under high-speed stirring at 1000r/min, uniformly stirring, adding the rest 20% of deionized water, uniformly stirring, discharging, filtering, and removing larger particles.
Example 5
The self-deposition coating comprises the following substances in percentage by mass:
(II) the preparation method comprises the following steps: weighing 80% of deionized water by weight, adding an emulsifier OP-10 into water under low-speed stirring at 200r/min, uniformly stirring, adding ethylene glycol butyl ether, a flatting agent, a wetting agent, a dispersing agent and a defoaming agent under medium-speed stirring at 500r/min, uniformly stirring, adding PVDC resin, SBR resin, water-based wax and color paste under high-speed stirring at 1000r/min, uniformly stirring, adding the rest 20% of deionized water, uniformly stirring, discharging, filtering, and removing larger particles.
Example 6
The self-deposition coating comprises the following substances in percentage by mass:
(II) the preparation method comprises the following steps: weighing 80% of deionized water by weight, adding an emulsifier OP-10 into water under low-speed stirring at 200r/min, uniformly stirring, adding benzyl alcohol, a flatting agent, a wetting agent, a dispersing agent and a defoaming agent under medium-speed stirring at 500r/min, uniformly stirring, adding PVDC resin, SBR resin, water-based wax and color paste under high-speed stirring at 1000r/min, uniformly stirring, adding the rest 20% of deionized water, uniformly stirring, discharging, filtering, and removing larger particles.
Example 7 autodeposition coating based on PVDC resin as main material, preparation method and application thereof
1. Preparation and construction process of autodeposition coating tank liquid
1) Pretreatment: sequentially degreasing, washing, pickling and washing with pure water for the steel substrate workpiece;
2) and (3) self-deposition:
adding water accounting for about 80% of the amount of the prepared tank into an acid-resistant and fluorine-resistant reaction tank with a temperature control and mechanical stirrer, respectively adding the autodeposition coating prepared in the examples 1-6 with the concentration of 15-20 wt% under the state of starting stirring, slowly adding 5% of self-made tank-opening agent after continuously stirring for 30min, and obtaining a deposition working solution after continuously stirring for 2 h.
The construction method comprises the following steps: immersion type
Stirring and controlling the temperature, wherein the temperature is set to be 20 +/-2 ℃;
tank concentration of autodeposition coating: 4-6 wt%;
the self-deposition time is as follows: 2.5-3 min;
oxidation-reduction potential: 350-450 mv.
3) Taking out the steel substrate workpiece after the self-deposition, drying the steel substrate workpiece at the single-stage low temperature of 75-85 ℃, cooling the steel substrate workpiece to room temperature, and directly depositing a layer of coating film on the steel substrate workpiece without reaction and water washing.
2. Performance detection
The results of comparing the effects of autodeposition coatings prepared in examples 1-6 of the present invention are shown in Table 1.
TABLE 1
As can be seen from Table 1, the solids content of the bath solution is directly related to the film thickness, and higher solids contents give better film thickness. The amount of wetting and leveling agents is increased, the film thickness is also reduced, but the appearance is smoother and smoother. The amount of SBR emulsion is increased, and the hardness of a paint film is increased. The process temperature and process time are both proportional to the film thickness.
3. Product stability test
The stability of the products was examined using the autodeposition coatings prepared in examples 1-6 and the results are given in Table 2.
TABLE 2
| Evaluation item | High temperature stability | Stability at Low temperature |
| Evaluation method | Keeping the temperature at 35 deg.C, and standing for 10 days under sealed packaging condition. | Do not examine |
| Evaluation criteria | The sample is uniform and stable, and no layering phenomenon exists; does not smell smelly | Do not examine |
As can be seen from Table 2, the stability of the product meets the requirements of conventional waterborne coatings.
The invention relates to an autodeposition coating based on PVDC resin as a main material, belonging to the technical field of metal coating. The experimental result shows that the autodeposition coating achieves good performance under the condition of no reaction water washing, the autodeposition coating is baked at low temperature, and the salt spray test reaches 700 hours. The system is stable and has no layering and caking phenomena.
Claims (5)
1. An autodeposition coating based on PVDC resin as a main material is characterized by comprising the following components in percentage by weight:
35 to 50 percent of PVDC resin liquid,
1 to 5 percent of SBR resin,
1 to 5 percent of water-based wax,
0.5 to 2 percent of emulsifier,
2 to 10 percent of film-forming additive,
0.1 to 0.3 percent of flatting agent,
0.5 to 2 percent of wetting agent,
0.2 to 1 percent of dispersant,
1 to 2 percent of color paste,
0.1 to 0.5 percent of defoaming agent,
The balance of water;
the emulsifier is one or a mixture of more than two of fatty alcohol-polyoxyethylene ether, isomeric tridecanol polyoxyethylene ether, alkyl sodium sulfonate, sodium alkyl benzene sulfonate, sodium dodecyl sulfate and alkylphenol polyoxyethylene ether;
the film-forming assistant is one or a mixture of more than two of propylene glycol methyl ether, propylene glycol phenyl ether, benzyl alcohol, dodecyl alcohol ester and ethylene glycol butyl ether.
2. The preparation method of the self-deposition coating based on PVDC resin as the main material, which is characterized by comprising the following steps: adding an emulsifier into water under medium-low speed stirring, uniformly stirring, then adding a film-forming auxiliary agent, a flatting agent, a wetting agent, a dispersing agent and a defoaming agent under medium-low speed stirring, uniformly stirring, then adding PVDC resin, SBR resin, water-based wax and color paste under medium-high speed stirring, and uniformly stirring.
3. The preparation method according to claim 2, wherein the medium-low speed stirring is 50 to 200 r/min; the medium-speed stirring is at 200-; the medium-high speed stirring is carried out at the speed of 800-2000 r/min.
4. The use of an autodeposition coating based on PVDC resin as a main material according to claim 1 in coating of steel-based workpieces.
5. Use according to claim 4, characterized in that the method is as follows:
1) pretreatment: sequentially degreasing, washing, pickling and washing with pure water for the steel substrate workpiece;
2) and (3) self-deposition: adding 4-6wt% of the self-deposition coating material based on PVDC resin as a main material according to claim 1 or 2, 3-10wt% of a jar opener and the balance of water in an acid-resistant fluorine-resistant reaction tank with a temperature control and mechanical stirrer, wherein the self-deposition coating material is obtained from a deposition working solution; immersing the pretreated steel substrate workpiece into an autodeposition working solution, setting the temperature to be 20 +/-2 ℃, and setting the autodeposition time to be 2.5-3 min;
3) taking out the steel substrate workpiece after the self-deposition, drying at 75-85 ℃, and cooling to room temperature.
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| CN201711180123.8A CN107955467B (en) | 2017-11-23 | 2017-11-23 | Self-deposition coating based on PVDC resin as main material and preparation method and application thereof |
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| CN201711180123.8A CN107955467B (en) | 2017-11-23 | 2017-11-23 | Self-deposition coating based on PVDC resin as main material and preparation method and application thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1054836A (en) * | 1989-12-15 | 1991-09-25 | 格雷斯公司 | Automatic deposition emulsion and the method for the metal surface being carried out selective protection with this emulsion |
| CN1090869A (en) * | 1992-09-23 | 1994-08-17 | 亨凯尔公司 | The aggregation group adulterant that is used for automatically deposited coating |
| US6312820B1 (en) * | 1983-07-25 | 2001-11-06 | Henkel Corporation | Vinylidene chloride resin in autodeposition |
-
2017
- 2017-11-23 CN CN201711180123.8A patent/CN107955467B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6312820B1 (en) * | 1983-07-25 | 2001-11-06 | Henkel Corporation | Vinylidene chloride resin in autodeposition |
| CN1054836A (en) * | 1989-12-15 | 1991-09-25 | 格雷斯公司 | Automatic deposition emulsion and the method for the metal surface being carried out selective protection with this emulsion |
| CN1090869A (en) * | 1992-09-23 | 1994-08-17 | 亨凯尔公司 | The aggregation group adulterant that is used for automatically deposited coating |
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