US3647567A - Post-dipping of acidic deposition coatings - Google Patents
Post-dipping of acidic deposition coatings Download PDFInfo
- Publication number
- US3647567A US3647567A US3647567DA US3647567A US 3647567 A US3647567 A US 3647567A US 3647567D A US3647567D A US 3647567DA US 3647567 A US3647567 A US 3647567A
- Authority
- US
- United States
- Prior art keywords
- acid
- water
- emulsion
- bath
- post
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- 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
- C09D5/088—Autophoretic paints
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
- Y10T428/31692—Next to addition polymer from unsaturated monomers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
- Y10T428/31692—Next to addition polymer from unsaturated monomers
- Y10T428/31699—Ester, halide or nitrile of addition polymer
Definitions
- This invention pertains to the deposition of coatings on a metal substrate and to the improvement in the properties of such coatings by a post-dipping process.
- the coating of metallic articles by acidic deposition is disclosed in copending patent application Ser. No. 880,914 filed Nov. 28, 1969.
- the acidic deposition process involves coating a metallic article from a bath which contains an oxidizing acid system and a synthetic film forming emulsion stabilized by nonionic or anionic surfactants.
- the oxidizing acid system must be capable of producing metal ions at the surface of the metallic article.
- the emulsion on the other hand, must be stable to this acid system 'but coagulatable onto the surface of the article by the action of the acid system produced metallic ions.
- Films prepared by acidic deposition generally contain at least a small amount of water soluble species along with various metal ions such as those of the substrate which has been coated. It is thought that these water soluble species contribute to the poor water and salt spray resistance often exhibited by acidic deposition films.
- This invention relates to an improvement in the acidic deposition process. Specifically it has been found that the resistance properties of acidic deposition films, especially to salt spray and water can be improved by contacting uh-baked or uncurred acidic deposited coatings with a solution of about 0.25 to 7.0 weight percent (based on the total solution weight) of a material selected from phosphoric acid (H P chromium trioxide (CrO and water or acid soluble chromates and dichromates. Following this step the acidic deposition films or coatings are then baked or dried according to standard methods.
- phosphoric acid H P chromium trioxide (CrO and water or acid soluble chromates and dichromates.
- Acidic deposition as referred to in this invention involves the addition of an oxidizing acid system to an aqueous emulsion (also called a latex or an aqueous polymeric dispersion) and the subsequent coagulation of this emulsion onto a metal substrate in the form of an adherent coating or film.
- aqueous emulsion also called a latex or an aqueous polymeric dispersion
- any aqueous, synthetic, resinous, film forming emulsion is satisfactory in forming the acidic deposition bath used therein.
- the emulsions used should be formed of vinyl or ethylenically polymerizable monomers.
- these emulsions be prepared in an aqueous medium by addition polymerization in the presence of anionic or nonionic surfactants or both.
- the preparation of these synthetic film forming emulsions can be accomplished by any of the standard emulsion processing techniques. Thus it is common to charge a portion of the polymerization catalysts or initiators into the reaction flask. The temperature of this mixture is then increased to about F.200 F. at which time separate additions of the remainder of the monomers and catalysts are carried out. Following these additions the emulsion mixture is held a reaction temperature until substantially complete monomer conversion is attained.
- Variations on this procedure include the use of a separate surfactant feed to be carried out during the monomer addition, the use of pre-emulsified monomers, the use of a water alcohol mixture as the emulsification medium and other well known variations.
- compositions of these emulsions can vary. Generally any of the normal emulsion monomers can be used.
- the vinyl esters of fatty acids having from 1 to 18 carbon atoms including vinyl acetate, vinyl propionate, vinyl butyrate, vinyl laurate, vinyl oleate, and vinyl stearate can be used.
- the various vinyl polymerizable acids such as acrylic, methacrylic, crotonic, itaconic and fumaric acids or maleic anhydride, etc., are useful.
- Esters of acrylic acid, methacrylic acid, maleic acid, or of other vinyl polymerizable acids with .alcohols, glycols or epoxides having from 1 to 18 carbon atoms can likewise be employed.
- esters examples include methyl acrylate or methacrylate, ethyl acrylate or methacrylate, propyl acrylate or methacrylate, isopropyl acrylate or methacrylate, the various butyl acrylyates or methacrylates, cyclohexyl, acrylate or methacrylate, berrzyl acrylate or methacrylate, isobornyl acrylate or methacrylate, phenyl acrylate or methacrylate, n-hexyl, n-octyl, 2-ethyl hexyl, t-octyl, dodecyl, hexadecyl, or octadecyl acrylates or methacrylates.
- Water resistance is expressed herein as percent water up-take. It is determined by immersing a baked coated panel in a bath of boiling water. The heat is then removed and the bath allowed to cool at room temperature for 3 hours. Prior to immersion in the bath, the panel is weighed and the area of its coated surface determined.
- various acid functional polymerizable monomers Preferred among these monomers are acrylic acid, methacrylic acid and itaconic acid. The incorporation of these acid monomers serve to improve film adhesion to the particular metallic substrate. However, if too large an amount of these acids is used, the water resistance of the resulting films can suffer. Therefore, it is desirable to have from about 0.25 weight percent to about 5.0- weight percent of these acids present based upon the total emulsion solids content.
- a Cross-linking monomer e.g., glycidyl methacrylates and acrylates, methylol functional monomers, e.g., methylol acrylamide or methacrylamide and alkylated methylol monomers, e.g., methylated, ethylated or butylated methylol acrylamide or methacrylamide.
- aqueous, emulsion, film forming compositions examples include:
- composition useful herein is a copolymer of about 0.5 to 15 weight percent of isobornyl methacrylate, about 0.5 to 10 weight percent of methylol acrylamide or methacrylamide, about to 60 weight percent of acrylonitrile or methacrylonitrile, about to 80 weight percent of a 1 to 8 carbon alcohol ester of an acid functional polymerizable monomer and about 0.25 to 5.0 weight percent of an acid functional polymerizable monomer.
- the emulsions as are useful in the processes of this invention can be either anionically or nonionically stabilized.
- the emulsion preferably should include, as one of its co-monomers, a polymerizable acid.
- any of the common nonionic surfactants can be used with advantage.
- These nonionic surfactants generally are polyethylene or polypropylene oxide derivatives having pendant hydrophobic groups such as phenoxy, or phenyl groups.
- Illus- 4 trative of these ethylene oxide or propylene oxide derived surfactants are the Igepals, which are members of an homologous series of alkylphenoxypoly(ethyleneoxy) ethanols, which can be represented by the general forwherein R represents an alkyl radical and n represents the number of mols of ethylene oxide employed.
- alkylphenoxypoly(ethyleneoxy) ethanols having alkyl groups containing from about 7 to about 18 carbon atoms inclusive, and having from about 4 to about ethyleneoxy units, such as the heptylphenoxypoly(ethyleneoxy) ethanols, nonylphenoxypoly (ethyleneoxy) ethanols and dodecylphenoxypoly(ethyleneoxy) ethanols; the sodium, potassium or ammonium salts of the sulfate esters of these alkylphenoxypoly(ethyleneoxy) ethanols; alkypoly(ethyleneoxy) ethanols; alkylpoly (propyleneoxy) ethanols octylphenoxyethoxy ethyldimethylbenzylammonium chloride; polyethylene glycol t-dodecylthioether; the Pluronics, which are condensates of ethylene oxide with a hydrophobic base, formed by condensing propylene oxide with propylene glycol; the Tritons;
- anionic stabilizers When anionically stabilized emulsions are prepared, the anionic stabilizers can be used alone or in admixture with the above nonionic surfactants. Generally any of the standard anionic stabilizers can be used in the emulsions herein prepared. These stabilizers (also called emulsifiers or surfactants) are salts--generally alkali metal salts of organic acids particularly the sulfates, phosphates or carboxylates. Examples include Triton 770 cone.
- co-reactive anionic surfactants which can be used either alone or in combination with nonionic surfactants, anionic surfactants or both.
- coereactive surfactants can be prepared by forming the alkali metal, amine or ammonia salt of sulfonic, phosphoric or carboxylic acids having sites of polymerizable unsaturation.
- Examples include the sodium salt of 2-sulfoethyl methacrylate, sodium vinyl sulfonate, the sodium salt of styrene sulfonic acid, as well as the sodium salts of the various polymerizable acids, e.g., acrylic acid, methacrylic acid, itaconic acid, maleic or fumaric acids, or ester acids, etc.
- the level of surfactant should be sufiicient to maintain emulsion stability in the presence of the dilute, oxidizing acid systems.
- the absolute amount of surfactant required can vary greatly. This amount is controlled by many factors including the emulsion monomers, polymer molecular weight, surfactant solubility, and surfactant unit charge.
- the preferred emul- HaCHzOH sions are prepared using the above described co-reactive surfactants. These surfactants can be used at very low levels (0.5 to and still produce oxidizing acid stable emulsions. In particular the use of these surfactants produces cured films having excellent water and solvent resistance properties.
- surfactants that can be used in preparing the emulsions of this invention preferably should not be substantially degraded in the presence of the dilute oxidizing acid systems.
- sugar saccharide, dextrose, etc.
- starch based surfactants are in many instances unsatisfactory as emulsion stabilizers for nitric acid containing acidic deposition baths.
- surfactants several systems are preferable. In one about 0.5 to 1.5 weight percent of the sodium salt of 2-sulfoethyl methacrylate based on the total emulsion solids is mixed with a like amount of sodium vinyl sulfonate. In another preferred system from about 0.25 to 1.5 percent of sodium lauryl sulfate is used. In yet another system a mixture of about 2.5 to 6.0 percent of an anionic phosphate surfactant is used. Finally, in another system, nonionic surfactants derived from nonylphenoxy poly(ethyleneoxy)ethanol are used.
- the monomers used herein are polymerized in the usual manner, i.e., by means of a catalytic amount of a conventional free radical polymerization catalyst or catalyst system (which can also be referred to as an addition polymerization catalyst, a vinyl polymerization catalyst or a polymerization initiator).
- a conventional free radical polymerization catalyst or catalyst system which can also be referred to as an addition polymerization catalyst, a vinyl polymerization catalyst or a polymerization initiator.
- An illustrative but by no means exhaustive enumeration of such catalysts includes inorganic peroxides such as hydrogen peroxide, sodium perchlorate and sodium perborate, inorganic persulfates such as sodium persulfate, potassium persulfate and ammonium persulfate, and redox systems such as sodium metabisulfite-potassium persulfate, and the like.
- initiators can be used. These include tertiary butyl hydroperoxide, benzoyl peroxide, tertiary butyl perbenzoate, tertiary butyl peroctoate, lauryl peroxide, azo-bis-isobutyronitrile (AIBN) and any of the other commonly used initiators.
- AIBN azo-bis-isobutyronitrile
- the emulsion which has previously been prepared is placed in a non-metallic container and an oxidizing acid system is added thereto.
- the solids of the resulting bath can vary from about 2% to about the solids level of the emulsion itself. However, when controlled film thicknesses are desired, it is preferred that the bath contain about 5-20% of the solid emulsion cop0lymerthe remainder being acid and water.
- the oxidizing acid systems which are used in this bath comprise those acid systems which act upon the particular metallic substrate to be coated producing a concentration of substrate metal ions at the bath-substrate interface sufficient to cause coagulation of the emulsion onto the metal.
- the metallic substrate contains iron, zinc or tin, nitric acid and in some cases sulfuric acid will cause the emulsions herein described to coagulate onto these substrata.
- Most preferred among the above acid systems is nitric acid.
- the substrate is either copper or aluminum more vigorous conditions are required. For example, by using a mixture of fiuoroboric acid, hydrofluoric acid, chromic anhydride and potassium ferricyanide either aluminum or copper can be coated by acidic deposition.
- This mixture can also coagulate emulsions onto normal iron, tin or Zinc type substrata.
- the amount of the oxidizing acid system that is used herein can vary depending on the stability of the particular emulsion and on the substrate that is to be coated. For example tin plate requires lower acid level baths than does steel. In general the amount of acid can vary from about 1.0% to 50% by weight based upon the solids weight of the emulsion that is used. Preferably this acid content should be in the 2.5 to 15 weight percent range.
- the preferred method of incorporating the desired acid system into these baths is to add the diluted emulsion to a solution of the oxidizing acid system, it is also possible to prepare the emulsions in the presence of the dilute acid system itself. This method then eliminates the necessity of post-adding acid to the diluted emulsion.
- any metallic substrate can be used in the process of this invention. Included are cold rolled steel, phosphatized steel, sand blasted steel, tin free steel, galvanized steel, iron, zinc, tin-plated steel, tin, copper, aluminum, etc.
- the only requirement of the substrate is that it produces sufiicient ions to coagulate the particular emulsion on its surface when it is immersed in the oxidizing acid system containing bath.
- tin is coated the most rapidly. For example, in a bath containing about 5 to 15 weight percent based on emulsion solids of nitric acid, a tin plated panel will be plated in about 10-40 seconds. On the other hand when steel panels are immersed in a bath containing a like amount of the same acid, plating can take from about 1 to 20 minutes.
- substrate coating can be carried out at room temperature or lower Without difficulty.
- the bath temperature can be increased to 50 C. or higher with a corresponding decrease in substrate plating time.
- the water resistance of the plated panels also increases.
- plating can be carried out between just above the freezing point of the bath and just below its boiling point.
- the baths as prepared herein can be used repeatedly to coat a large number of metal articles.
- a 10% solids emulsion bath placed in a 500 ml. beaker can be used to plate as many as 150 or more 3" x 6" steel panels.
- the bath emulsion solids tends to decrease while the bath pH increases.
- additional amounts of the acid system and the emulsion must periodically be introduced into the coating bath.
- residual metal ion content in the bath increases due to the surface dissolution of the metallic articles.
- This metal ion content can be controlled by any conventional means of metallic ion separation, e.g., electrodeposition, precipitation, ion exchange, etc.
- the process herein disclosed is not limited to the coating of metal panels.
- car bodies, siding material, appliance bodies, metal containers, or any other metallic substrate can be coated with advantage.
- a metal tank or container can be coated by pumping the bath as described above into this container and then removing the bath after a coating of sufl'icient thickness is obtained.
- any metallic substrate can be coated simply by contacting it With the baths herein prepared.
- the emulsions of this invention can be formed into paints.
- the pigments which are useful, however, are preferably limited to those pigments which are nonreactive with oxidizing acid systems.
- pigmented emulsions can be employed to coat metallic articles by the processes described herein in the same manner that non-pigmented emulsions can be used.
- the coated metal articles are contacted with the solution described hereinafter, preferably washed with water, and then either air dried or baked using standard methods.
- the substrate is baked at a low temperature (about F.l75 F.) for about 1 minute to 25 minutes. This step allows the removal of water trapped in the coated films.
- a higher temperature bake (about 225 F. to 400 F.) is carried out over a like period to insure complete cure of the coating.
- cure is used herein it is meant ot be synonymous with crosslinking or drying.
- any solvent which will solvate the materials hereinafter described can be used with the proviso that this solvent not act to dissolve the acidic deposition films during immersion.
- this solvent it is preferred that a major portion of the solvent be water.
- the active portion of this post-dipping bath is about 0.25 to about 7.0 weight percent (based upon the total post-dip bath content) of a material selected from chromium trioxide, phosphoric acid, and water soluble or acid soluble chromates and dichromates. Included among these materials are the following chromates; potassium, sodium, ammonium, calcium, cesium, lithium, magnesium, zinc, etc., and dichromates; sodium, ammonium, lithium, etc. Preferred among these chromates and dichromates is zinc chromate.
- phosphoric acid When phosphoric acid is used in the post-dipping bath it is preferred that it be added to the bath at about the 0.25 to 3.0 weight percent level.
- this level preferably can range from 0.25 to 5.0 percent. Most preferable results, in general, are obtained when any of the above bath materials are present at about the 0.5 to 1.5 weight percent level.
- the amount of time that the uncured or unbaked acidic deposited film is exposed to this bath can vary from about seconds to 5-10 minutes. However it is preferred that hath exposure generally be in the 90 seconds range. Exposures of greater than 15 or minutes generally cause redispersion of the uncured film and result in baked films which are highly discolored.
- the unbaked acidic deposited :films can be exposed to the above bath by any convenient method.
- a tank or container which has been coated by acidic deposition can be subjected to this bath by pumping the bath solution into the container itself.
- this bath can be applied by spraying or brushing.
- the preferred method of bringing the acidic deposited, coated metal substrate into contact with this bath is by dipping.
- ferrous ions Fe++
- ferric ions Fe+++
- Fe o Fe Hzr These metal ions in turn can act to coagulate the emulsion. Since this coagulation effect occurs at the interface of the metallic article and the emulsion, a film of the emulsion is thereby deposited onto the surface of the metallic article.
- An acidic deposition bath was prepared by adding 40 ml. of the above emulsion to 150 ml. of water and 10 ml. of a 10% aqueous nitric acid solution. Seven duplicate sets of panels Were dipped in the above bath for five minutes producting uniform coatings thereon. Immediately after the coating process, one of the coated panels from each set was dipped for 30 seconds in water while the other panel of the set was dipped for 30 seconds in a 0.5% aqueous chromium trioXide solution. Both panels were then baked for 5 minutes at F. followed by 5 minutes at 300 F. The water uptake of all panels was determined with the following results.
- EXAMPLE 2 from each set was then immersed in a 1% aqueous phosphorie acid solution for 30 seconds and then baked for 5 minutes at 140 F. followed by 5 minutes at 300 F.
- the other panel in each set was baked as above immediately after its removal from the acidic deposition bath. Water up-take was evaluated with the following results:
- EXAMPLE 3 An emulsion was prepared as described in Example 1. An acidic deposition bath was prepared by adding 20 ml. of this emulsion to 10 ml. of a 5% aqueous nitric acid solution and 70 ml. of water. A zinc chromate containing solution was prepared by adding an excess of zinc carbonate to a 10% aqueous chromium trioxide solution. For a 3.0% zinc chromate post-dip bath 60 ml. of this zinc chromate-chromium trioxide solution were added to 140 ml. of water. For a 0.5% post-dip solution 10 ml. were added to 190 ml. of water.
- EXAMPLE 4 Using the same procedure as described in Example 1, an emulsion was prepared which exhibited a #1 spindle, 20 r.p.m., Brookfield viscosity of 23 cps., essentially no free monomer, a pH of 2.90 and a solids content of 48.5% (48.1% theoretical). At the same time a pigment paste was prepared comprising 12 parts of a mixture of magnesium silicate and calcium silicate, 24 parts of barytes, 24 parts of red iron oxide, 24.0 parts of water, 1.6 parts of Daxad 30, an anionic surfactant derived from the sodium salt of a polymerized carboxylic acid obtained from W. R.
- An acid deposition bath was prepared by mixing 10 ml. of a 10% aqueous nitric acid solution, 10 ml. of the above pigment paste, 20 ml. of, the above emulsion and 60 ml. of water.
- a cold rolledsteel panel was dipped into this bath for minutes and then dipped into a bath containing 0.5 weight percent chromium trioxide. This panel was then baked for 15 minutes at 140 F. followed by 15 minutes at 300 F.
- a red coating resulted which had excellent appearance and exhibited a water up-take of 2.41%.
- EXAMPLE 5 Using the same procedure as in Example 1, a similar emulsion was prepared except that #3 contained 90 additional grams of water, and 16.2 additional grams of itaconic acid and that #4 contained 16.2 less grams of butyl acrylate. The resulting emulsion exhibited a solids content of 45.6% (47.0% theoretical), less than 0.2 free monomer, a density of 1.03 g./ml. and a pH of 3.05.
- a ml. acidic deposition bath was prepared by mixing 20 ml. of the above emulsion with 5 ml. of a 10 weight percent aqueous nitric acid solution and 75 ml. of water. Six pairs of cold rolled steel panels were dipped in this bath for 5 minutes. Out of each pair one was dipped in a bath containing 10 ml. of a 10% by weight aqueous chromium trioxide solution and 190 ml. of water. Both the dipped and the non-dipped panels were then baked for 5 minutes at F. followed by 5 minutes at 300 F. Water up-take tests were performed on each set of panels with the following results:
- Chromate Set post-dip EXAMPLE 6 An emulsion was prepared according to Example 1. 600 ml. of this emulsion were added to a mixture of 2250 ml. of water and ml. of a 10% aqueous nitric acid solution. In addition a 0.5% chromate bath was prepared by adding 5 grams of chromium trioxide to 1000 grams of water. 2 sets of cold rolled steel panels were coated for 5 minutes in the above acidic deposition bath. Out of each set one panel was dipped for 30 seconds in the chromate post dip solution and baked with the non-post-dipped P31861501 5 minutes at 140 F. followed by 5 minutes at 3 The first set of panels were placed in 70 C. salt spray for 24 hours and removed.
- the chromate post-dipped panel showed little evidence of degradation.
- the non-post-dipped panel was completely blistered and discolored after this period of salt spray.
- the postdipped panel was kept in salt spray for 23 additional hours before substantial film degradation occurred. But even after this 47 hours of total salt spray exposure no blistering of the film was evident.
- the second set of panels as prepared above-one nonpost-dipped and one post-dipped was placed in boiling water. After 2 hours immersion the film on the postdipped panel was still tough with no evidence of discoloration. However, after only /2 hours immersion in boiling water, the film on the non-post-dipped panel was severely discolored. One hours immersion resulted in a bubbling of the film while after 1 /2 hours immersion, the non-post-dipped film peeled off its steel substrate.
- EXAMPLE 7 Using the same procedure as in Example 1 a similar emulsion was prepared except that part #4 contained 629 grams of butyl acetate, 59 grams of isobornyl methacrylate, and 368 grams of 'acrylonitrile. The resulting emulsion exhibited a solids content of 47.6% (47.7% theoretical), and a percent monomer conversion of 9916-.
- An acidic deposition bath was prepared by adding 20 ml. of the above emulsion to 5 ml. of a 10% aqueous nitric acid solution and 75 ml. of water. Two sets of steel panels were dipped in the above bath for 5 minutes and one set was post-dipped for 30 seconds in a 1.0 weight percent chromium trioxide solution while the other set was dipped for a like amount of time in a 3.0 weight percent chromium trioxide solution. These panels were then baked Percent Chromium Water trioxide up-take Film appearance and general water resistance were excellent.
- An improvement in the process of coating metallic articles by acidic deposition which comprises:
- An improvement in the process of coating metallic articles by acidic deposition which comprises:
Abstract
Description
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US88098169A | 1969-11-28 | 1969-11-28 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3647567A true US3647567A (en) | 1972-03-07 |
Family
ID=25377534
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US3647567D Expired - Lifetime US3647567A (en) | 1969-11-28 | 1969-11-28 | Post-dipping of acidic deposition coatings |
Country Status (2)
Country | Link |
---|---|
US (1) | US3647567A (en) |
AT (1) | AT301978B (en) |
Cited By (53)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3839097A (en) * | 1972-05-26 | 1974-10-01 | Amchem Prod | Stabilization of acidic aqueous coating compositions containing an organic coating-forming material |
US3865617A (en) * | 1971-08-11 | 1975-02-11 | Toyota Motor Co Ltd | Method of coating by redox polymerization |
US3936546A (en) * | 1971-06-14 | 1976-02-03 | Amchem Products, Inc. | Prolonging the stability of coating baths |
DE2719558A1 (en) * | 1976-05-04 | 1977-11-17 | Nippon Paint Co Ltd | METAL SURFACE TREATMENT METHOD |
US4138276A (en) * | 1976-03-01 | 1979-02-06 | J. M. Eltzroth & Associates, Inc. | Coating compositions |
US4170671A (en) * | 1977-05-03 | 1979-10-09 | Nippon Paint Co., Ltd. | Method for treatment of metal surface |
US4180603A (en) * | 1977-01-31 | 1979-12-25 | Oxy Metal Industries Corporation | Coating bath composition and method |
US4186226A (en) * | 1978-06-21 | 1980-01-29 | Union Carbide Corporation | Autodeposited coatings with increased surface slip |
US4190468A (en) * | 1977-08-15 | 1980-02-26 | Nippon Steel Corporation | Process for coating an electrical steel sheet with an anti-sticking layer |
US4214022A (en) * | 1975-05-30 | 1980-07-22 | Akzo N.V. | Coating metal by immersion |
US4215162A (en) * | 1975-05-30 | 1980-07-29 | Akzo N.V. | Process of coating metal surfaces |
US4229492A (en) * | 1977-12-30 | 1980-10-21 | Amchem Products, Inc. | Control of autodeposition baths |
US4255305A (en) * | 1977-01-31 | 1981-03-10 | Oxy Metal Industries Corporation | Coating bath composition and method |
US4357372A (en) * | 1977-12-30 | 1982-11-02 | Amchem Products, Inc. | Control of autodeposition baths |
US4411950A (en) * | 1978-06-21 | 1983-10-25 | Amchem Products, Inc. | Autodeposited coatings with increased surface slip |
US4562098A (en) * | 1983-07-25 | 1985-12-31 | Amchem Products Inc. | Water or steam cure of autodeposited resin coatings on metallic substrates |
US4636264A (en) * | 1985-01-09 | 1987-01-13 | Gerhard Collardin Gmbh | Autodeposition post-bath rinse process |
US4636265A (en) * | 1984-11-26 | 1987-01-13 | Henkel Kommanditgesellschaft Auf Aktien | Autodeposition post-bath rinse |
US4637839A (en) * | 1975-08-29 | 1987-01-20 | Amchem Products, Inc. | Treating autodeposited coating with Cr composition |
US4647480A (en) * | 1983-07-25 | 1987-03-03 | Amchem Products, Inc. | Use of additive in aqueous cure of autodeposited coatings |
US4657788A (en) * | 1986-03-31 | 1987-04-14 | The Standard Oil Company | Process for multiple stage autodeposition of organic coatings onto metals |
US4800106A (en) * | 1987-06-19 | 1989-01-24 | Amchem Products, Inc. | Gloss enhancement of autodeposited coatings |
US5114751A (en) * | 1989-10-24 | 1992-05-19 | Henkel Corporation | Application of an organic coating to small metal articles |
US5164234A (en) * | 1991-01-24 | 1992-11-17 | Henkel Corporation | Treating an autodeposited coating with an alkaline solution containing organophosphonate ions |
US5248525A (en) * | 1991-01-24 | 1993-09-28 | Henkel Corporation | Treating an autodeposited coating with an alkaline solution containing anions of multifunctional organic acids |
US5342694A (en) * | 1983-07-25 | 1994-08-30 | Henkel Corporation | Treating an autodeposited coating with an alkaline material |
US5688560A (en) * | 1993-11-09 | 1997-11-18 | Henkel Corporation | Process for coating metal surfaces |
US6143365A (en) * | 1998-06-03 | 2000-11-07 | Henkel Corporation | Autodeposited coating with improved thermal stability and composition and process therefor |
WO2000071265A1 (en) | 1999-05-21 | 2000-11-30 | Henkel Corporation | Autodeposition post-bath rinse process |
US20020011309A1 (en) * | 2000-02-18 | 2002-01-31 | Agarwal Rajat K. | Rubber-metal Composites |
US20030104212A1 (en) * | 1999-05-26 | 2003-06-05 | Agarwal Rajat K. | Epoxy resin-based autodeposition coatings |
US6613387B2 (en) | 2000-11-22 | 2003-09-02 | Henkel Corporation | Protective reaction rinse for autodeposition coatings |
US20040220058A1 (en) * | 2002-09-06 | 2004-11-04 | Eoff Larry S. | Compositions and methods of stabilizing subterranean formations containing reactive shales |
US20040229757A1 (en) * | 2003-05-16 | 2004-11-18 | Eoff Larry S. | Methods and compositions for reducing the production of water and stimulating hydrocarbon production from a subterranean formation |
US20040229756A1 (en) * | 2003-05-16 | 2004-11-18 | Eoff Larry S. | Method for stimulating hydrocarbon production and reducing the production of water from a subterranean formation |
US20050164894A1 (en) * | 2004-01-24 | 2005-07-28 | Eoff Larry S. | Methods and compositions for the diversion of aqueous injection fluids in injection operations |
US20050194140A1 (en) * | 2003-05-16 | 2005-09-08 | Halliburton Energy Services, Inc. | Methods useful for diverting aqueous fluids in subterranean operations |
US20050199396A1 (en) * | 2003-05-16 | 2005-09-15 | Leopoldo Sierra | Methods useful for controlling fluid loss in subterranean treatments |
US20050230116A1 (en) * | 2004-04-15 | 2005-10-20 | Eoff Larry S | Methods and compositions for use with spacer fluids used in subterranean well bores |
US20060137875A1 (en) * | 2003-05-16 | 2006-06-29 | Halliburton Energy Services, Inc. | Methods useful for controlling fluid loss in subterranean formations |
US20060266522A1 (en) * | 2003-05-16 | 2006-11-30 | Halliburton Energy Services, Inc. | Methods useful for controlling fluid loss during sand control operations |
US20060283592A1 (en) * | 2003-05-16 | 2006-12-21 | Halliburton Energy Services, Inc. | Method useful for controlling fluid loss in subterranean formations |
US7398825B2 (en) | 2004-12-03 | 2008-07-15 | Halliburton Energy Services, Inc. | Methods of controlling sand and water production in subterranean zones |
US20080173448A1 (en) * | 2007-01-19 | 2008-07-24 | Halliburton Energy Services, Inc. | Methods for treating intervals of a subterranean formation having variable permeability |
US7493957B2 (en) | 2005-07-15 | 2009-02-24 | Halliburton Energy Services, Inc. | Methods for controlling water and sand production in subterranean wells |
US20090090056A1 (en) * | 2007-10-09 | 2009-04-09 | Greatpoint Energy, Inc. | Compositions for Catalytic Gasification of a Petroleum Coke |
US20090120642A1 (en) * | 2007-11-14 | 2009-05-14 | Halliburton Energy Services, Inc. | Methods to enhance gas production following a relative-permeability-modifier treatment |
US20090253594A1 (en) * | 2008-04-04 | 2009-10-08 | Halliburton Energy Services, Inc. | Methods for placement of sealant in subterranean intervals |
US20100186954A1 (en) * | 2005-07-15 | 2010-07-29 | Nguyen Phillip D | Methods for controlling water and particulate production in subterranean wells |
US20100216672A1 (en) * | 2009-02-24 | 2010-08-26 | Halliburton Energy Services, Inc. | Treatment fluids comprising relative permeability modifiers and methods of use |
US20110034351A1 (en) * | 2009-08-10 | 2011-02-10 | Eoff Larry S | Hydrophobically and Cationically Modified Relative Permeability Modifiers and Associated Methods |
US7934557B2 (en) | 2007-02-15 | 2011-05-03 | Halliburton Energy Services, Inc. | Methods of completing wells for controlling water and particulate production |
US8962535B2 (en) | 2003-05-16 | 2015-02-24 | Halliburton Energy Services, Inc. | Methods of diverting chelating agents in subterranean treatments |
-
1969
- 1969-11-28 US US3647567D patent/US3647567A/en not_active Expired - Lifetime
-
1970
- 1970-11-25 AT AT1061370A patent/AT301978B/en active
Cited By (78)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3936546A (en) * | 1971-06-14 | 1976-02-03 | Amchem Products, Inc. | Prolonging the stability of coating baths |
US3865617A (en) * | 1971-08-11 | 1975-02-11 | Toyota Motor Co Ltd | Method of coating by redox polymerization |
US3839097A (en) * | 1972-05-26 | 1974-10-01 | Amchem Prod | Stabilization of acidic aqueous coating compositions containing an organic coating-forming material |
US4214022A (en) * | 1975-05-30 | 1980-07-22 | Akzo N.V. | Coating metal by immersion |
US4215162A (en) * | 1975-05-30 | 1980-07-29 | Akzo N.V. | Process of coating metal surfaces |
US4637839A (en) * | 1975-08-29 | 1987-01-20 | Amchem Products, Inc. | Treating autodeposited coating with Cr composition |
US4138276A (en) * | 1976-03-01 | 1979-02-06 | J. M. Eltzroth & Associates, Inc. | Coating compositions |
DE2719558A1 (en) * | 1976-05-04 | 1977-11-17 | Nippon Paint Co Ltd | METAL SURFACE TREATMENT METHOD |
US4180603A (en) * | 1977-01-31 | 1979-12-25 | Oxy Metal Industries Corporation | Coating bath composition and method |
US4255305A (en) * | 1977-01-31 | 1981-03-10 | Oxy Metal Industries Corporation | Coating bath composition and method |
US4170671A (en) * | 1977-05-03 | 1979-10-09 | Nippon Paint Co., Ltd. | Method for treatment of metal surface |
US4190468A (en) * | 1977-08-15 | 1980-02-26 | Nippon Steel Corporation | Process for coating an electrical steel sheet with an anti-sticking layer |
US4357372A (en) * | 1977-12-30 | 1982-11-02 | Amchem Products, Inc. | Control of autodeposition baths |
US4229492A (en) * | 1977-12-30 | 1980-10-21 | Amchem Products, Inc. | Control of autodeposition baths |
US4186226A (en) * | 1978-06-21 | 1980-01-29 | Union Carbide Corporation | Autodeposited coatings with increased surface slip |
US4411950A (en) * | 1978-06-21 | 1983-10-25 | Amchem Products, Inc. | Autodeposited coatings with increased surface slip |
US4562098A (en) * | 1983-07-25 | 1985-12-31 | Amchem Products Inc. | Water or steam cure of autodeposited resin coatings on metallic substrates |
US5342694A (en) * | 1983-07-25 | 1994-08-30 | Henkel Corporation | Treating an autodeposited coating with an alkaline material |
US4647480A (en) * | 1983-07-25 | 1987-03-03 | Amchem Products, Inc. | Use of additive in aqueous cure of autodeposited coatings |
US4636265A (en) * | 1984-11-26 | 1987-01-13 | Henkel Kommanditgesellschaft Auf Aktien | Autodeposition post-bath rinse |
US4636264A (en) * | 1985-01-09 | 1987-01-13 | Gerhard Collardin Gmbh | Autodeposition post-bath rinse process |
US4657788A (en) * | 1986-03-31 | 1987-04-14 | The Standard Oil Company | Process for multiple stage autodeposition of organic coatings onto metals |
US4800106A (en) * | 1987-06-19 | 1989-01-24 | Amchem Products, Inc. | Gloss enhancement of autodeposited coatings |
US5114751A (en) * | 1989-10-24 | 1992-05-19 | Henkel Corporation | Application of an organic coating to small metal articles |
US5248525A (en) * | 1991-01-24 | 1993-09-28 | Henkel Corporation | Treating an autodeposited coating with an alkaline solution containing anions of multifunctional organic acids |
US5164234A (en) * | 1991-01-24 | 1992-11-17 | Henkel Corporation | Treating an autodeposited coating with an alkaline solution containing organophosphonate ions |
US5688560A (en) * | 1993-11-09 | 1997-11-18 | Henkel Corporation | Process for coating metal surfaces |
US6143365A (en) * | 1998-06-03 | 2000-11-07 | Henkel Corporation | Autodeposited coating with improved thermal stability and composition and process therefor |
US6410092B1 (en) | 1999-05-21 | 2002-06-25 | Henkel Corporation | Autodeposition post-bath rinse process |
WO2000071265A1 (en) | 1999-05-21 | 2000-11-30 | Henkel Corporation | Autodeposition post-bath rinse process |
US20030104212A1 (en) * | 1999-05-26 | 2003-06-05 | Agarwal Rajat K. | Epoxy resin-based autodeposition coatings |
US6833398B2 (en) * | 1999-05-26 | 2004-12-21 | Henkel Kommanditgesellschaft Auf Aktien | Epoxy resin-based autodeposition coatings |
US20020011309A1 (en) * | 2000-02-18 | 2002-01-31 | Agarwal Rajat K. | Rubber-metal Composites |
US6805768B2 (en) | 2000-02-18 | 2004-10-19 | Henkel Kommanditgesellschaft Auf Aktien | Method of forming rubber-metal composites |
US6613387B2 (en) | 2000-11-22 | 2003-09-02 | Henkel Corporation | Protective reaction rinse for autodeposition coatings |
EP1339504A1 (en) * | 2000-11-22 | 2003-09-03 | Henkel Kommanditgesellschaft auf Aktien | Protective reaction rinse for autodeposition coatings |
EP1339504A4 (en) * | 2000-11-22 | 2004-03-31 | Henkel Kgaa | Protective reaction rinse for autodeposition coatings |
US20040220058A1 (en) * | 2002-09-06 | 2004-11-04 | Eoff Larry S. | Compositions and methods of stabilizing subterranean formations containing reactive shales |
US7741251B2 (en) | 2002-09-06 | 2010-06-22 | Halliburton Energy Services, Inc. | Compositions and methods of stabilizing subterranean formations containing reactive shales |
US20040229757A1 (en) * | 2003-05-16 | 2004-11-18 | Eoff Larry S. | Methods and compositions for reducing the production of water and stimulating hydrocarbon production from a subterranean formation |
US20040229756A1 (en) * | 2003-05-16 | 2004-11-18 | Eoff Larry S. | Method for stimulating hydrocarbon production and reducing the production of water from a subterranean formation |
US8962535B2 (en) | 2003-05-16 | 2015-02-24 | Halliburton Energy Services, Inc. | Methods of diverting chelating agents in subterranean treatments |
US20050194140A1 (en) * | 2003-05-16 | 2005-09-08 | Halliburton Energy Services, Inc. | Methods useful for diverting aqueous fluids in subterranean operations |
US20050199396A1 (en) * | 2003-05-16 | 2005-09-15 | Leopoldo Sierra | Methods useful for controlling fluid loss in subterranean treatments |
US8631869B2 (en) | 2003-05-16 | 2014-01-21 | Leopoldo Sierra | Methods useful for controlling fluid loss in subterranean treatments |
US20060137875A1 (en) * | 2003-05-16 | 2006-06-29 | Halliburton Energy Services, Inc. | Methods useful for controlling fluid loss in subterranean formations |
US8278250B2 (en) | 2003-05-16 | 2012-10-02 | Halliburton Energy Services, Inc. | Methods useful for diverting aqueous fluids in subterranean operations |
US8251141B2 (en) | 2003-05-16 | 2012-08-28 | Halliburton Energy Services, Inc. | Methods useful for controlling fluid loss during sand control operations |
US20060266522A1 (en) * | 2003-05-16 | 2006-11-30 | Halliburton Energy Services, Inc. | Methods useful for controlling fluid loss during sand control operations |
US20060283592A1 (en) * | 2003-05-16 | 2006-12-21 | Halliburton Energy Services, Inc. | Method useful for controlling fluid loss in subterranean formations |
US8181703B2 (en) | 2003-05-16 | 2012-05-22 | Halliburton Energy Services, Inc. | Method useful for controlling fluid loss in subterranean formations |
US8091638B2 (en) | 2003-05-16 | 2012-01-10 | Halliburton Energy Services, Inc. | Methods useful for controlling fluid loss in subterranean formations |
US7759292B2 (en) | 2003-05-16 | 2010-07-20 | Halliburton Energy Services, Inc. | Methods and compositions for reducing the production of water and stimulating hydrocarbon production from a subterranean formation |
US7595283B2 (en) | 2004-01-20 | 2009-09-29 | Halliburton Energy Services, Inc. | Methods and compositions for reducing the production of water and stimulating hydrocarbon production from a subterranean formation |
US20060234874A1 (en) * | 2004-01-20 | 2006-10-19 | Halliburton Energy Services, Inc. | Methods and compositions for reducing the production of water and stimulating hydrocarbon production from a subterranean formation |
US8008235B2 (en) | 2004-01-20 | 2011-08-30 | Halliburton Energy Services, Inc. | Permeability-modifying drilling fluids and methods of use |
US20060240994A1 (en) * | 2004-01-20 | 2006-10-26 | Halliburton Energy Services, Inc. | Methods and compositions for reducing the production of water and stimulating hydrocarbon production from a subterranean formation |
US7589048B2 (en) | 2004-01-20 | 2009-09-15 | Halliburton Energy Services, Inc. | Methods and compositions for reducing the production of water and stimulating hydrocarbon production from a subterranean formation |
US20050155796A1 (en) * | 2004-01-20 | 2005-07-21 | Eoff Larry S. | Permeability-modifying drilling fluids and methods of use |
US20050164894A1 (en) * | 2004-01-24 | 2005-07-28 | Eoff Larry S. | Methods and compositions for the diversion of aqueous injection fluids in injection operations |
US7563750B2 (en) | 2004-01-24 | 2009-07-21 | Halliburton Energy Services, Inc. | Methods and compositions for the diversion of aqueous injection fluids in injection operations |
US20050230116A1 (en) * | 2004-04-15 | 2005-10-20 | Eoff Larry S | Methods and compositions for use with spacer fluids used in subterranean well bores |
US7398825B2 (en) | 2004-12-03 | 2008-07-15 | Halliburton Energy Services, Inc. | Methods of controlling sand and water production in subterranean zones |
US7493957B2 (en) | 2005-07-15 | 2009-02-24 | Halliburton Energy Services, Inc. | Methods for controlling water and sand production in subterranean wells |
US20100186954A1 (en) * | 2005-07-15 | 2010-07-29 | Nguyen Phillip D | Methods for controlling water and particulate production in subterranean wells |
US7730950B2 (en) | 2007-01-19 | 2010-06-08 | Halliburton Energy Services, Inc. | Methods for treating intervals of a subterranean formation having variable permeability |
US20080173448A1 (en) * | 2007-01-19 | 2008-07-24 | Halliburton Energy Services, Inc. | Methods for treating intervals of a subterranean formation having variable permeability |
US7934557B2 (en) | 2007-02-15 | 2011-05-03 | Halliburton Energy Services, Inc. | Methods of completing wells for controlling water and particulate production |
US20090090056A1 (en) * | 2007-10-09 | 2009-04-09 | Greatpoint Energy, Inc. | Compositions for Catalytic Gasification of a Petroleum Coke |
US20090120642A1 (en) * | 2007-11-14 | 2009-05-14 | Halliburton Energy Services, Inc. | Methods to enhance gas production following a relative-permeability-modifier treatment |
US7552771B2 (en) | 2007-11-14 | 2009-06-30 | Halliburton Energy Services, Inc. | Methods to enhance gas production following a relative-permeability-modifier treatment |
US20100116498A1 (en) * | 2008-04-04 | 2010-05-13 | Dalrymple Eldon D | Methods for Placement of Sealant in Subterranean Intervals |
US8272440B2 (en) | 2008-04-04 | 2012-09-25 | Halliburton Energy Services, Inc. | Methods for placement of sealant in subterranean intervals |
US20090253594A1 (en) * | 2008-04-04 | 2009-10-08 | Halliburton Energy Services, Inc. | Methods for placement of sealant in subterranean intervals |
US7998910B2 (en) | 2009-02-24 | 2011-08-16 | Halliburton Energy Services, Inc. | Treatment fluids comprising relative permeability modifiers and methods of use |
US20100216672A1 (en) * | 2009-02-24 | 2010-08-26 | Halliburton Energy Services, Inc. | Treatment fluids comprising relative permeability modifiers and methods of use |
US20110034351A1 (en) * | 2009-08-10 | 2011-02-10 | Eoff Larry S | Hydrophobically and Cationically Modified Relative Permeability Modifiers and Associated Methods |
US8420576B2 (en) | 2009-08-10 | 2013-04-16 | Halliburton Energy Services, Inc. | Hydrophobically and cationically modified relative permeability modifiers and associated methods |
Also Published As
Publication number | Publication date |
---|---|
AT301978B (en) | 1972-09-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3647567A (en) | Post-dipping of acidic deposition coatings | |
US3709743A (en) | Acidic deposition process | |
US3922451A (en) | Coated beverage container and process of coating | |
US3883453A (en) | Coating compositions containing acrylic polymers polymerized in the presence of cellulose acetate butyrate | |
US5342694A (en) | Treating an autodeposited coating with an alkaline material | |
US3503918A (en) | Aqueous dispersion of thermosettable acrylonitrile copolymers and articles coated therewith | |
US3617368A (en) | Process for preparing inherently colloidally stable interpolymers in aqueous dispersion and products coated therewith | |
US4103049A (en) | Process for applying resinous coating to metal surface | |
US4373050A (en) | Process and composition for coating metals | |
US2918391A (en) | Resinous coating composition, method of preparing and method of coating with same | |
EP0295713B1 (en) | Gloss enhancement of autodeposited coatings | |
EP0132828B1 (en) | Vinylidene chloride latex in autodeposition and low temperature cure | |
US5352726A (en) | Autodepositing composition containing vinylidene chloride based resin | |
US4104424A (en) | Process for coating metals | |
US3036934A (en) | Coated article and method of making same | |
US4874673A (en) | Use of fugitive plasticizer in autodepositing composition | |
US3655426A (en) | Process of coating metal with polyvinyl fluoride and resultant product | |
US3328330A (en) | Vinylidene chloride copolymer latices | |
US4657788A (en) | Process for multiple stage autodeposition of organic coatings onto metals | |
US4160756A (en) | Use of metal compound in an autodeposition coating composition | |
EP0071355B1 (en) | Corrosion resistant autodeposition coatings | |
US6224947B1 (en) | Process for forming a resinous coating from an autodepositing composition which includes internally stabilized vinylidene chloride copolymer | |
US5912297A (en) | Internally stabilized vinylidene chloride resin in autodeposition | |
EP0186113A2 (en) | Use of fugitive plasticizer in autodepositing composition | |
US3282867A (en) | Water base interpolymer coatings |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: INTEREZ, INC.,STATELESS Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:CELANESE CORPORATION, A CORP. OF DE.;REEL/FRAME:004599/0982 Effective date: 19860715 Owner name: INTEREZ, INC. Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:CELANESE CORPORATION, A CORP. OF DE.;REEL/FRAME:004599/0982 Effective date: 19860715 |
|
AS | Assignment |
Owner name: INTEREZ, INC., A CORP. OF GA Free format text: MERGER;ASSIGNOR:INTEREZ, INC., A CORP. OF DE (MERGED INTO);REEL/FRAME:004756/0154 Effective date: 19861230 |