CA1092264A - Coating galvanized wire - Google Patents
Coating galvanized wireInfo
- Publication number
- CA1092264A CA1092264A CA268,063A CA268063A CA1092264A CA 1092264 A CA1092264 A CA 1092264A CA 268063 A CA268063 A CA 268063A CA 1092264 A CA1092264 A CA 1092264A
- Authority
- CA
- Canada
- Prior art keywords
- acid
- composition
- tannin
- polymers
- zinc
- 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
Links
Classifications
-
- 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
- B05D7/16—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 using synthetic lacquers or varnishes
-
- 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
- B05D7/20—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 wires
-
- 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
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
- C09D5/086—Organic or non-macromolecular compounds
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Chemical Treatment Of Metals (AREA)
- Paints Or Removers (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Disclosed are a composition and process useful for forming a corrosion resistant coating having good adhesion and drying properties on a zinc alloy surface. The composition employed is an aqueous composition (solution or dispersion) containing an organic film-forming resin on a tannin material. When galvanized wire is contacted with the composition, a uniform, corrosion-resistant coating is obtained having improved adhesion to the galvanized surface. Pretreat-mant with a conversion coating solution is not required.
Disclosed are a composition and process useful for forming a corrosion resistant coating having good adhesion and drying properties on a zinc alloy surface. The composition employed is an aqueous composition (solution or dispersion) containing an organic film-forming resin on a tannin material. When galvanized wire is contacted with the composition, a uniform, corrosion-resistant coating is obtained having improved adhesion to the galvanized surface. Pretreat-mant with a conversion coating solution is not required.
Description
~09~6~
The present invention relate3 to a proce~s for form-ing a protective coating on the surface of galvanized steel wire.
When a zinc or zinc alloy ~urface is coated with an aqueous solution or dispersion of a water-soluble or water-dis-persible organic polymer resin, there will normally be for~ed on the surface thereof oxides of zinc or zinc soaps which re-sult, for example, from the reaction of zinc with carboxyl ra-dicals in the resin or in the surface active agent used for dispersing and stabilizing the resin, pigments or other bath components. The adhesion of the resulting coating i~ very poor. It has thus been necessary when treating galvanized steel wire with an aqueous solution or dispersion containing a water-soluble or water-dispersible organic polymer resin to first treat the wire by a process of chemical conversion (e.g., chromic acid or zinc phosphate process).
~; When a metal surface i8 coated with an aqueouq solu-tion or dispersion of a water-soluble or dispersible organic polymer resin, the coating cannot be dried easily due to the higher latent heat of vaporization and higher boiling point of water as compared to conventional coating in organic ~ol-vents such as thinner, toluene, xylene, etc. Further, when applied on a material having a circular cro~s section such as wire, aqueous coatings tend to have the disadvantage of forming pools of the coating at the lower part of the coated articles.
It has now been found that a protective coating having good corrosion re~istance, adhesion and drying pro-perties may be obtained from an aqueous solution or disper-sion of a water-soluble or water dispersible film-forming organic polymer resin without pretreatment by a chemical con-version process by including tannin or tannic acid (tannin ~ -,, material) in an amount ranging from 0.1 to 20% hy weight, preferably from 1 to 5% by weight in the treating solution or dispersion.
The water-soluble or dispersible organic polymer resins useful in this invention include substantially all type~ of conventionally available film-forming organic resins, Thus one or more aqueous solutions and/or emulsions and/or suspensions may be usable in this invention which contain one or more water-soluble, emulsifiable or dispersible organic resins such as, for example, vinylic polymers and copolymers of vinyl acetate, vinyl chloride, and vinylidene chloride, -polymers and copolymers of acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters, hydroxyacrylic acid, and hydroxymethacrylic acid, alkyd-, epoxy-, fluorine-containing,urethane, polyester, styrene, and olefinic poly-mers and copolymers, ~ynthetic rubber such as butadiene rubber, and naturally occurring organic polymers. For colora-tion, inorganic pigments such as titanium dioxide, carbon, aluminum paste, iron oxides, molybdic acid yellow, zinc dust, and organic dyes or pigments such as Phthalocyanine Blue, Phthalocyanine Green, Benzidine Yellow and Naphthol Yellow, may be included in the composition.
The concentration in the treating solution of the polymer employed will normally be less than 40 wt. % solids and typically between 5 and 30 wt. %.
In o~der to improve the film forming property of the water-soluble or dispersible organic polymer resin, the aqueous solutions or dispersions according to thi~ invention may include, for example, a pla~ticizer such as a phthalate ester, aliphatic dibasic acid ester, glycol ester, fatty acid ester, phosphoric acid ester, epoxy plasticizer, trioctyl ,' "' , ~ ~ .". ,' ' '~'. ', ' ,,.' .' .'''' " ' .
trimellitate, butylphthalyl butyl glycolate, tributyl acetyl citrate, chlorinated paraffin, polypropylene adipate, poly-propylene sebacate or the like and a high boiling solvent selected from ketones, esters and glycols such as cellosolve or butyl glycol. In addition, the aqueous solutions or dis-persion may include, if required, surfactants such as a dis-persing agent, wetting agent, antifungal agent, defoaming agent or the like.
Tannins or tannic acids useful in thiq invention may be hydrolyzable or condensed tannins or partially decomposed products thereof and include, for example, dep~ide tannin, gallotannin, Chinese tannic acid, Turkey tannic acid, hamameli-tannic acid, tannic acid from Acer Ginnala, chebulinic acid, sumac, Chinese gallotannin, ellagitannin, catechin, quebracho and the like. m e aqueous solution or dispersion of this in-vention may be prepared conventionally, for example, by dis-solving tannin or tannic acid in water, adding the resulting tannic solution to an aqueous solution or dispersion of a water-soluble or dispersible organic polymer resin and agitat-ing the mixture. The concentration of tannin or tannic aciddepends on the types of tannin but ranges generally from 0.1 to 20% by weight.
At a concentration of lower than 0.1% by weight of tannin or tannic acid, the adhesion property of the coating can be improved but the effect for improving the drying pro-perty of coating is poor. At a concentration of higher than 20% by weight, the coating composition is unfavorable because of poor opera~ility and economics.
In order to improve the adhesion of the protective coating and to stabilize the treating medium containing tannin, when the pH of the medium is adjusted, there may be added an inorganic acid ~uch as phosphoric acid, sulfuric . . . . . ..
.
acid, nitric acid, hydrofluoric acid, or the like, or a salt thereof, or an organic acid such as oxalic acid, citric acid, malic acid, maleic acid, phthalic acid, acetic acid, lactic acid, tartaric acid, chloroacetic acid, acrylic acid or the like or a salt thereof, or an alkaline compound such as ~odium hydroxide, potassium hydroxide, lithium hydroxide or the like, or an amine such as ammonia, ethyl amine, kiethyl amine, tri-ethyl amine, ethanol amine or the like.
The pH value of the treating liquid according to this invention depends on the applying procedures and types of tannin or tannic acid, resin, pigments and the like, but ran-ges generally from 2.5 to 9.5, preferably from 3.5 to 7Ø
The treating liquid of this invention may be applied onto the zinc or zinc alloy surface by immersion, roll coating, flooding, spraying, electrostatic coating, brushing or the like.
The present invention will be now illustrated by way of the following examples.
60 parts of Chinese gallotannin (available from Fuji Chemical Industries Co., Ltd. under the name of Tannic Acid AL) was dissolved in 440 parts of deionized water.
Separately, 500 parts of acrylic acid ester emulsion (concen-tration of solid resin: 40% by weight, available from Toyo Ink Co. Ltd. under the trademark Tocryl N-142) was combined with 100 parts of Phtalocyanine Blue pigment lnonvolatile matter: 37%, available from Toyo Ink Co. Ltd. under the name of E.M. Blue 2G) and mixed thoroughly to prepare a homoge-neous dispersion. m e dispersion was mixed with the previous-ly prepared tannin solution and the mixture was di~persed homogeneously by means of a propéller agitator. When diluted with deionized water of pH 6.5 to a dilution of 10 time~, it had a pH of 3.5. Commercially available hot galvanized steel wire was polished by means of steel wool and then pas~ed through cotton cloth impregnated with the treating liquid to be coated therewith. After drying one minute at room temperature in a horizontal position, the coating could not be manually peeled off and was of uniform thicknes~ and color and exhibited no evidence of dense pooling of the treating chemicals on the bottom horizontal surface.
On the contrary, when identical galvanized steel wire was coated with a similar solution to the above-mentioned liquid but containing no Chinese gallotannin, the resulting coating was still wet one minute after the application and wa~
of non-uniform thickness and coloration.
60 parts of the above Chinese gallotannin was dis-solved in 440 parts of deionized water and the pH of the re-sulting solution was adjusted to 7.0 by adding 28% aqueous ammonia. The pH-adjusted solution was then combined with 450 -parts of a water-soluble polyolefin resin (non-volatile mat-ter: 25%, available from Seitetsu Chemicals Co. Ltd. under the trade mark of Zaikthene-A) and 50 parts of carbon black (non-volatile matter: 40%, available from Toyo Ink Co. Ltd. --under the trade mark of EM Black-K) and dispersed homogeneously to prepare the treating liquid. m e resin is a water ~oluble copolymer containing 9 moles of ethylene per mole of acrylic acid, has a molecular weight range of 100,000-150,000, and a ~-25% aqueous solution has a vi~co~ity of 50-100 cps.
When diluted with deionized water having a pH of 6.5 to a dilution of 10 times, it had a pH of 7.3. Commer-cially available hot galvanized steel wire having a diameter lU5~ZZ6~
of 2.0 mm was polished by means of steel wool and then immer~-ed in~o the preparation at room temperature (20 - 25C). The treated wire was blown with hot air at about 80 to 120C to remove the excess preparation and dry the surface. When the colored galvanized steel was wound around a pipe having a diameter of lO mm, no peeling of the coating was observed.
On the contrary, when identical galvanized steel wire was treated with a similar treating liquid but containing no tannin, the coating was peeled off during drying and when the coated wire was wound around a pipe having a diameter of 10 mm, 50% of the colored coating was peeled off.
The present invention relate3 to a proce~s for form-ing a protective coating on the surface of galvanized steel wire.
When a zinc or zinc alloy ~urface is coated with an aqueous solution or dispersion of a water-soluble or water-dis-persible organic polymer resin, there will normally be for~ed on the surface thereof oxides of zinc or zinc soaps which re-sult, for example, from the reaction of zinc with carboxyl ra-dicals in the resin or in the surface active agent used for dispersing and stabilizing the resin, pigments or other bath components. The adhesion of the resulting coating i~ very poor. It has thus been necessary when treating galvanized steel wire with an aqueous solution or dispersion containing a water-soluble or water-dispersible organic polymer resin to first treat the wire by a process of chemical conversion (e.g., chromic acid or zinc phosphate process).
~; When a metal surface i8 coated with an aqueouq solu-tion or dispersion of a water-soluble or dispersible organic polymer resin, the coating cannot be dried easily due to the higher latent heat of vaporization and higher boiling point of water as compared to conventional coating in organic ~ol-vents such as thinner, toluene, xylene, etc. Further, when applied on a material having a circular cro~s section such as wire, aqueous coatings tend to have the disadvantage of forming pools of the coating at the lower part of the coated articles.
It has now been found that a protective coating having good corrosion re~istance, adhesion and drying pro-perties may be obtained from an aqueous solution or disper-sion of a water-soluble or water dispersible film-forming organic polymer resin without pretreatment by a chemical con-version process by including tannin or tannic acid (tannin ~ -,, material) in an amount ranging from 0.1 to 20% hy weight, preferably from 1 to 5% by weight in the treating solution or dispersion.
The water-soluble or dispersible organic polymer resins useful in this invention include substantially all type~ of conventionally available film-forming organic resins, Thus one or more aqueous solutions and/or emulsions and/or suspensions may be usable in this invention which contain one or more water-soluble, emulsifiable or dispersible organic resins such as, for example, vinylic polymers and copolymers of vinyl acetate, vinyl chloride, and vinylidene chloride, -polymers and copolymers of acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters, hydroxyacrylic acid, and hydroxymethacrylic acid, alkyd-, epoxy-, fluorine-containing,urethane, polyester, styrene, and olefinic poly-mers and copolymers, ~ynthetic rubber such as butadiene rubber, and naturally occurring organic polymers. For colora-tion, inorganic pigments such as titanium dioxide, carbon, aluminum paste, iron oxides, molybdic acid yellow, zinc dust, and organic dyes or pigments such as Phthalocyanine Blue, Phthalocyanine Green, Benzidine Yellow and Naphthol Yellow, may be included in the composition.
The concentration in the treating solution of the polymer employed will normally be less than 40 wt. % solids and typically between 5 and 30 wt. %.
In o~der to improve the film forming property of the water-soluble or dispersible organic polymer resin, the aqueous solutions or dispersions according to thi~ invention may include, for example, a pla~ticizer such as a phthalate ester, aliphatic dibasic acid ester, glycol ester, fatty acid ester, phosphoric acid ester, epoxy plasticizer, trioctyl ,' "' , ~ ~ .". ,' ' '~'. ', ' ,,.' .' .'''' " ' .
trimellitate, butylphthalyl butyl glycolate, tributyl acetyl citrate, chlorinated paraffin, polypropylene adipate, poly-propylene sebacate or the like and a high boiling solvent selected from ketones, esters and glycols such as cellosolve or butyl glycol. In addition, the aqueous solutions or dis-persion may include, if required, surfactants such as a dis-persing agent, wetting agent, antifungal agent, defoaming agent or the like.
Tannins or tannic acids useful in thiq invention may be hydrolyzable or condensed tannins or partially decomposed products thereof and include, for example, dep~ide tannin, gallotannin, Chinese tannic acid, Turkey tannic acid, hamameli-tannic acid, tannic acid from Acer Ginnala, chebulinic acid, sumac, Chinese gallotannin, ellagitannin, catechin, quebracho and the like. m e aqueous solution or dispersion of this in-vention may be prepared conventionally, for example, by dis-solving tannin or tannic acid in water, adding the resulting tannic solution to an aqueous solution or dispersion of a water-soluble or dispersible organic polymer resin and agitat-ing the mixture. The concentration of tannin or tannic aciddepends on the types of tannin but ranges generally from 0.1 to 20% by weight.
At a concentration of lower than 0.1% by weight of tannin or tannic acid, the adhesion property of the coating can be improved but the effect for improving the drying pro-perty of coating is poor. At a concentration of higher than 20% by weight, the coating composition is unfavorable because of poor opera~ility and economics.
In order to improve the adhesion of the protective coating and to stabilize the treating medium containing tannin, when the pH of the medium is adjusted, there may be added an inorganic acid ~uch as phosphoric acid, sulfuric . . . . . ..
.
acid, nitric acid, hydrofluoric acid, or the like, or a salt thereof, or an organic acid such as oxalic acid, citric acid, malic acid, maleic acid, phthalic acid, acetic acid, lactic acid, tartaric acid, chloroacetic acid, acrylic acid or the like or a salt thereof, or an alkaline compound such as ~odium hydroxide, potassium hydroxide, lithium hydroxide or the like, or an amine such as ammonia, ethyl amine, kiethyl amine, tri-ethyl amine, ethanol amine or the like.
The pH value of the treating liquid according to this invention depends on the applying procedures and types of tannin or tannic acid, resin, pigments and the like, but ran-ges generally from 2.5 to 9.5, preferably from 3.5 to 7Ø
The treating liquid of this invention may be applied onto the zinc or zinc alloy surface by immersion, roll coating, flooding, spraying, electrostatic coating, brushing or the like.
The present invention will be now illustrated by way of the following examples.
60 parts of Chinese gallotannin (available from Fuji Chemical Industries Co., Ltd. under the name of Tannic Acid AL) was dissolved in 440 parts of deionized water.
Separately, 500 parts of acrylic acid ester emulsion (concen-tration of solid resin: 40% by weight, available from Toyo Ink Co. Ltd. under the trademark Tocryl N-142) was combined with 100 parts of Phtalocyanine Blue pigment lnonvolatile matter: 37%, available from Toyo Ink Co. Ltd. under the name of E.M. Blue 2G) and mixed thoroughly to prepare a homoge-neous dispersion. m e dispersion was mixed with the previous-ly prepared tannin solution and the mixture was di~persed homogeneously by means of a propéller agitator. When diluted with deionized water of pH 6.5 to a dilution of 10 time~, it had a pH of 3.5. Commercially available hot galvanized steel wire was polished by means of steel wool and then pas~ed through cotton cloth impregnated with the treating liquid to be coated therewith. After drying one minute at room temperature in a horizontal position, the coating could not be manually peeled off and was of uniform thicknes~ and color and exhibited no evidence of dense pooling of the treating chemicals on the bottom horizontal surface.
On the contrary, when identical galvanized steel wire was coated with a similar solution to the above-mentioned liquid but containing no Chinese gallotannin, the resulting coating was still wet one minute after the application and wa~
of non-uniform thickness and coloration.
60 parts of the above Chinese gallotannin was dis-solved in 440 parts of deionized water and the pH of the re-sulting solution was adjusted to 7.0 by adding 28% aqueous ammonia. The pH-adjusted solution was then combined with 450 -parts of a water-soluble polyolefin resin (non-volatile mat-ter: 25%, available from Seitetsu Chemicals Co. Ltd. under the trade mark of Zaikthene-A) and 50 parts of carbon black (non-volatile matter: 40%, available from Toyo Ink Co. Ltd. --under the trade mark of EM Black-K) and dispersed homogeneously to prepare the treating liquid. m e resin is a water ~oluble copolymer containing 9 moles of ethylene per mole of acrylic acid, has a molecular weight range of 100,000-150,000, and a ~-25% aqueous solution has a vi~co~ity of 50-100 cps.
When diluted with deionized water having a pH of 6.5 to a dilution of 10 times, it had a pH of 7.3. Commer-cially available hot galvanized steel wire having a diameter lU5~ZZ6~
of 2.0 mm was polished by means of steel wool and then immer~-ed in~o the preparation at room temperature (20 - 25C). The treated wire was blown with hot air at about 80 to 120C to remove the excess preparation and dry the surface. When the colored galvanized steel was wound around a pipe having a diameter of lO mm, no peeling of the coating was observed.
On the contrary, when identical galvanized steel wire was treated with a similar treating liquid but containing no tannin, the coating was peeled off during drying and when the coated wire was wound around a pipe having a diameter of 10 mm, 50% of the colored coating was peeled off.
Claims (7)
1. An aqueous composition useful for treating a zinc or zinc alloy surface comprising an organic film-forming polymer and from 0.1 to 20 wt. % of a tannin material.
2. The composition of claim 1 wherein the polymer concen-tration is not in excess of 40 wt. % and the concentration of the tannin material is between 1 and 5 wt. %.
3. The composition of claim 1 wherein the polymer is selected from the group of film-forming polymers consisting of vinylic polymers and copolymers of vinyl acetate, vinyl chloride, and vinylidene chloride, polymers and copolymers of acrylic acid, methacrylic acid, acrylic acid esters, metha-crylic acid esters, hydroxyacrylic acid, and hydroxymetha-crylic acid; alkyd-, epoxy-, fluorine-containing, urethane, polyester, styrene and olefinic polymers and copolymers, synthetic rubber, and naturally occurring organic polymers.
4. The composition of claim 3 wherein the polymer is butadiene rubber.
5. The composition of claim 4 wherein the tannin material is selected from the group consisting of depside tannin, gallo-tannin, Chinese tannic acid, Turkey tannic acid, hamamelitannic acid, tannic acid from Acer Ginnala, chebulinic acid, sumac, Chinese gallotannin, ellagitannin, catechin and quebracho.
6. The composition of claim 1 containing at least one adjuvant selected from the group consisting of pigments, plas-ticizers, high boiling organic solvents and surfactants.
7. A process for forming an adhesive corrosion resistant coating having good drying properties on a zinc or zinc alloy surface comprising contacting the surface with the composi-tion of claim 1 and thereafter drying the surface.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP149556/75 | 1975-12-17 | ||
| JP14955675A JPS5273136A (en) | 1975-12-17 | 1975-12-17 | Process for forming protective coating on zinc plated steel wires |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1092264A true CA1092264A (en) | 1980-12-23 |
Family
ID=15477737
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA268,063A Expired CA1092264A (en) | 1975-12-17 | 1976-12-16 | Coating galvanized wire |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPS5273136A (en) |
| AU (1) | AU510275B2 (en) |
| CA (1) | CA1092264A (en) |
| GB (1) | GB1556869A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53133537A (en) * | 1977-04-27 | 1978-11-21 | Daiwa Kasei Kenkyusho:Kk | Rust preventives for zinc and zinc alloy |
| US4313861A (en) * | 1980-02-28 | 1982-02-02 | Union Carbide Corporation | Latex autodeposition coatings |
| GB2075538B (en) * | 1980-05-02 | 1983-12-21 | Applied Coating Tech Inc | Stable latex rust converting primer |
| DE3269806D1 (en) * | 1981-07-24 | 1986-04-17 | Scott Bader Co | Corrosion resistant autodeposition coatings |
| JPS61212368A (en) * | 1985-03-15 | 1986-09-20 | Nippon Steel Corp | Rust-preventive coating method for plated wire rod |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5247535A (en) * | 1975-10-15 | 1977-04-15 | Nippon Steel Corp | Process for forming rusttproofing underlayer on metallic articles |
-
1975
- 1975-12-17 JP JP14955675A patent/JPS5273136A/en active Pending
-
1976
- 1976-12-14 GB GB5205076A patent/GB1556869A/en not_active Expired
- 1976-12-15 AU AU20580/76A patent/AU510275B2/en not_active Expired
- 1976-12-16 CA CA268,063A patent/CA1092264A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| AU2058076A (en) | 1978-06-22 |
| GB1556869A (en) | 1979-11-28 |
| AU510275B2 (en) | 1980-06-19 |
| JPS5273136A (en) | 1977-06-18 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |