WO2002064856A1 - Metal surface-treatment agents, metal surface-treatment method and surface-treated metal materials - Google Patents

Metal surface-treatment agents, metal surface-treatment method and surface-treated metal materials Download PDF

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Publication number
WO2002064856A1
WO2002064856A1 PCT/JP2002/001214 JP0201214W WO02064856A1 WO 2002064856 A1 WO2002064856 A1 WO 2002064856A1 JP 0201214 W JP0201214 W JP 0201214W WO 02064856 A1 WO02064856 A1 WO 02064856A1
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Prior art keywords
resin
aqueous
metal surface
mass
aqueous dispersion
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PCT/JP2002/001214
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English (en)
Japanese (ja)
Inventor
Motohiro Sasaki
Koichi Saito
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Nippon Paint Co., Ltd.
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Application filed by Nippon Paint Co., Ltd. filed Critical Nippon Paint Co., Ltd.
Publication of WO2002064856A1 publication Critical patent/WO2002064856A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • 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
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/06—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • C08L23/0884—Epoxide containing esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

  • the present invention relates to a metal surface treatment agent, a metal surface treatment method and a surface-treated metal material, and more particularly to an ionomer-based resin-based aqueous dispersion.
  • a metal surface treatment agent comprising: Background art
  • a method of using an aqueous dispersion of ionomer resin obtained by neutralizing a copolymer of ethylene and an unsaturated carboxylic acid with metal ions is known.
  • This ionomer resin has good adhesion to various base materials, especially metals, and the formed film is tough and resistant to scratches, and is resistant to solvents such as ethanol, methyl, and ethyl ketone. It is a material with excellent properties.
  • aqueous dispersion composition formed by mixing a polyvalent epoxy compound at a temperature of 50 ° C. or less with an ionomer resin as a base (Japanese Patent Application Laid-Open No. Hei 4-131 478). No.). Furthermore, a metal-based metal-containing metal-coating agent containing an ionomer resin neutralized with a divalent metal such as magnesium or zinc has been proposed (JP-A-11-111).
  • a film formed of the above-mentioned ionomer resin or a composition based on the ionomer resin has insufficient conductivity when the film thickness is large, and necessarily has good paint adhesion when a top coat is applied. Can not get.
  • the present invention has been made in view of the above problems, and particularly when used as a surface treatment agent on a zinc-coated steel sheet, corrosion resistance can be ensured, the conductivity of the film is excellent, and overcoating is performed on the film.
  • An object of the present invention is to provide a metal surface treatment agent, a metal surface treatment method, and a surface treated metal material having excellent paint adhesion when a paint is applied.
  • An aqueous composition containing 0.1 to 0.5% by mass of the carboxyl group of an ethylene-unsaturated carboxylic acid copolymer containing 10 to 30% by mass of an unsaturated carboxylic acid containing 10 to 30% by mass of an unsaturated carboxylic acid.
  • the metal surface treating agent as described above comprising a composite aqueous dispersion resin obtained by radical polymerization of an unsaturated monomer in the presence of the aqueous dispersion resin.
  • a composite aqueous dispersion resin obtained by radical polymerization of an unsaturated monomer in a mixture of the aqueous dispersion resin and at least one aqueous resin selected from an aqueous polyurethane resin, an aqueous polyester resin, and an aqueous acryl resin.
  • a metal surface treatment agent comprising a mixture.
  • a metal surface treatment method comprising applying the metal surface treatment agent to the surface of a metal material to form a film.
  • the aqueous dispersion resin has a solid content concentration of 5 to 30% by mass, and the fine silica particles have a mass of 1 to 10%. /.
  • Ethylene monounsaturated power containing 0 to 30% by mass Neutralize 30% or more of the carboxyl groups of the rubonic acid copolymer with the use of a force-ream ion. This is an aqueous dispersion obtained by the above method.
  • Examples of the unsaturated carboxylic acid of the present invention include atrialic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid and the like, and acrylic acid and methacrylic acid are particularly preferable.
  • the ionomer resin of the present invention uses potassium as an ion source.
  • the ion source is another monovalent ion, for example, sodium
  • the formed film has insufficient conductivity.
  • the ion source is a divalent ion, for example, zinc or magnesium, the conductivity is not sufficient.
  • the ionomer resin of the present invention has a neutrality of carboxyl groups due to potassium ions of 30% or more.
  • the degree of neutralization is less than 30%, the conductivity is not sufficient, and when the degree of neutralization is extremely low, the solvent resistance decreases.
  • the upper limit of the degree of neutralization is not particularly limited, but is preferably within 100% from the viewpoint of corrosion resistance.
  • an aqueous dispersion resin is formed by reacting the aqueous dispersion of the ionomer resin with an epoxy compound, and a metal surface treating agent containing the aqueous dispersion resin is obtained.
  • the epoxy compound refers to a compound having at least one epoxy group in one molecule, and includes glycidyl ethers and glycidyl esters.
  • Glycidyl ethers include, for example, phenyldaricidyl ether, resonole syndiglycidyl ether, bisphenol A diglycidyl ether ', glycerol Polyglycidyl 'ether, trimethylo-propane polyglycidinoleate ether, pentaerythritol polyglycidyl ether and the like.
  • the dalicidyl esters include diglycidyl adipate and diglycidyl phthalate.
  • the reaction between the ionomer resin and the epoxy compound is carried out at a temperature in the range of 30 ° C to boiling point, more preferably at a temperature in the range of 60 to 95 ° C. If the temperature is lower than 30 ° C, the reaction will not proceed sufficiently.
  • the reaction time is 0.5 to 10 hours.
  • the metal surface treating agent is excellent in conductivity of a film when used as a metal surface treating agent, and is excellent in coating adhesion when a top coat is formed on the film.
  • the metal surface treating agent of the present invention is obtained by further mixing silica fine particles with the above water-dispersible resin.
  • the silica fine particles are not particularly limited, but for example, those having an average particle size of about 0.01 to 0.5 ⁇ m are suitable, and are appropriately selected from colloidal silica, fumed silica, and the like. Can be used. It is preferable that the silica fine particles be blended in an amount of 1 to 10% by mass.
  • the metal surface treating agent of the present invention is obtained by further mixing a thiocarbonyl group-containing compound as an organic inhibitor with the above aqueous composition.
  • thiocarbonyl group-containing compound examples include thioperia, sodium dimethyldithiocarbamate, 1,3-bis (dimethylaminopropyl) -12-thioperia, pentamethylenedithio-capillate pyruvate, and pyridine.
  • Pipecholine dithiocarbamate 1,3 diphenylthioperire, ethylenethioperea, propylenethiourea, feninorethiolea, 1,3 dibutylthiopererea, 1,3 methylthiopererea, trimethylthiopererea, thioacetamide, thioacetamide, thiocarbohydrazide , Ethylene tridithiocarbonate, dimethyldithiocarbamate triethylamine salt, methyldithiopotassium sodium rubamate, polyethylene xanthate acid rim, and the like.
  • the thiocarbonyl group-containing compound is preferably incorporated in an amount of 0.02 to 5% by mass.
  • the metal surface treating agent of the present invention is obtained by further mixing phosphate ions with the above aqueous composition.
  • Examples of the phosphate ion source include diammonium hydrogen phosphate.
  • the metal surface treating agent of the present invention comprises a mixture of the above-mentioned silica fine particles, a thiocarbonyl group-containing compound, and a phosphate ion, whereby the zinc-plated steel sheet surface-treated with the metal surface treating agent is subjected to chromate treatment. It can be made equivalent to the case. Further, the metal surface treating agent is excellent in the conductivity of a film when used as a surface treating agent, and is excellent in coating adhesion when an overcoat film is formed on the film.
  • the metal surface treating agent thus obtained can be further compounded or blended with another resin in the aqueous dispersion resin.
  • a composite aqueous dispersion resin of an ionomer-based aqueous dispersion resin and an acryl resin can be obtained by subjecting an unsaturated monomer to radical polymerization using an initiator in the presence of the aqueous dispersion resin.
  • At least one aqueous resin selected from an aqueous polyurethane resin, an aqueous polyester resin, and an aqueous ataryl resin may be further blended with the aqueous dispersion resin or the composite aqueous dispersion resin.
  • aqueous dispersion resin a mixture of the above aqueous dispersion resin and at least one aqueous resin selected from an aqueous polyurethane resin, an aqueous polyester resin, and an aqueous acryl resin
  • radical polymerization of an unsaturated monomer is carried out to form a composite aqueous dispersion. It may be a mixture.
  • alkyl (meth) acrylates, styrene, (meth) acrylic acid, hydroxyanolequinole (meth) acrylates, (meth) acrylic acid, and the like are used. be able to.
  • polymerization initiator examples include persulfates such as potassium persulfate and ammonium persulfate, and azo compounds such as azobiscyanovaleric acid and azobisdisoptyronitrile.
  • the aqueous polyurethane resin may be prepared, for example, by converting a diol into a diamine such as hexamethylene diisocyanate, isophorone diisocyanate, or tolylene diisocyanate. It can be obtained by reacting with a succinate compound, further extending the chain with diamine or the like, and dispersing in water.
  • a diol such as hexamethylene diisocyanate, isophorone diisocyanate, or tolylene diisocyanate. It can be obtained by reacting with a succinate compound, further extending the chain with diamine or the like, and dispersing in water.
  • the aqueous polyester resin can be obtained by, for example, dehydrating and condensing a diol and a polybasic acid, neutralizing the resultant with an amine or the like, and making it water-soluble or water-dispersed.
  • the aqueous acrylic resin is prepared, for example, by radically polymerizing an unsaturated monomer containing an unsaturated carboxylic acid in an organic solvent, and then neutralizing the radical with an amine or the like to make it water-soluble or dispersed in water. And a method of subjecting the unsaturated monomer to emulsion polymerization.
  • the other resin to be compounded or compounded is used as a solid content in an amount of 50 parts by mass or less, more preferably 30 parts by mass or less, based on 100 parts by mass of the aqueous dispersion resin before compounding or compounding. .
  • the metal surface treatment agent obtained as described above can improve the corrosion resistance of a film when used as a surface treatment agent. If the amount of the composite or compound exceeds 50% by mass, the effect of improving the conductivity of the obtained metal surface treating agent is impaired.
  • the radical polymerization conditions for obtaining the above composite aqueous dispersion are such that the reaction temperature is 40 to 90 ° (the reaction time is 0.5 to 0.5 hours; L 0 hour).
  • the above-mentioned metal surface treatment agent is applied to the surface of a metal material to form a film.
  • the coating method is not particularly limited, and a normal coating method such as a roll coating method, a spray method, and immersion can be used.
  • the film formed by the above metal surface treatment method has excellent conductivity and corrosion resistance, and also has excellent solvent resistance.
  • a top coat is applied on the above-mentioned film to form a coated film.
  • the coating method is not particularly limited, and a normal coating method such as a roll coating method, a spray method, and a dipping method can be used.
  • the surface-treated metal material obtained by the above-described metal surface treatment method has excellent coating adhesion of the topcoat.
  • BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be further described with reference to Examples and Comparative Examples. Note that the present invention is not limited to the embodiments described below.
  • Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Primaco 59801 100 80 70
  • the metal surface treating agents of Examples and Comparative Examples were Primacor 59801 (acrylic acid content of 20% by Dow Chemical, 20% by mass) as an ethylene-acrylic acid copolymer, and replacement paper (Rule 26). 9
  • Potassium hydroxide was used as a potassium ion source in the examples. Further, as a metal ion source of a comparative example, sodium hydroxide was used as a monovalent sodium ion source, and zinc oxide was used as a divalent zinc ion source. In some Examples and Comparative Examples, ammonia, which is a volatile neutralizer, was used in combination with a metal ion source, or was used instead of a metal ion source.
  • Epoxy compounds of the examples include denacol 313 (glycerin polyglycidyl ether Teragase Kasei Kogyo), denacol 321 (trimethylolpropane polyglycidyl ether Nagase Kasei Kogyo), or epiquat 828 (bisphenol).
  • a diglycidyl ether manufactured by Yuka Shell Epoxy was used.
  • Adekabon Titer-1 H U X-320 manufactured by Asahi Denka Kogyo was used.
  • the unsaturated monomers used in forming the composite aqueous dispersion were those shown in Table 1.
  • KPS is potassium persulfate as a polymerization initiator.
  • the particle size comprises 2 0 mass 0/0 1 0 to 2 0 nm colloidal silica as a solid content, Snowtex N (manufactured by Nissan Chemical Industries) Was.
  • Examples and Comparative Examples of the surface-treated metal material the compounds shown in Tables 2 to 5 were used as the thiocarbonyl group-containing compounds to be blended with each of the above components. Also, a phosphate ion source was blended.
  • Trietinoleamine salt (0.25) ⁇
  • the preparation method of the metal surface treating agent using each of the above-mentioned raw materials was based on the following method.
  • a predetermined amount of metal ion source, a predetermined amount of 25% by mass ammonia water for some examples and comparative examples, and a slightly different amount of deionized water for each example and comparative example It was charged and maintained at a temperature of 95 ° C. for 2 hours with stirring. Thereafter, the mixture was cooled with water to obtain an aqueous dispersion having a different neutralization ratio for each of Examples and Comparative Examples.
  • the solids content of this aqueous dispersion is uniformly adjusted to 22% by mass in all of the Examples and Comparative Examples by presetting the amount of deionized water to a slightly different amount for each Example or Comparative Example. ing.
  • Example 2 an aqueous polyurethane resin was further added to the aqueous dispersion resin.
  • Example 3 an unsaturated monomer was polymerized in the presence of the aqueous dispersion resin.
  • Example 4 an unsaturated monomer was polymerized in a mixture of the aqueous dispersion resin and the aqueous polyurethane resin.
  • Polymerization of the unsaturated monomer was performed as follows. First, half of the value of the unsaturated monomer shown in Table 1 was poured into a flask containing an aqueous dispersion resin maintained at 80 ° C while stirring, and after 10 minutes, a 1% aqueous solution of persulfuric acid aqueous solution was added. Was added in an amount 2/3 of the value shown in Table 1 to start the reaction. After a further 10 minutes, the remaining unsaturated monomer was added, and then, after a further 10 minutes, the remaining 1% aqueous persulfuric acid aqueous solution was added, and then the temperature was maintained at 80 ° C for 2 hours. The reaction was completed.
  • aqueous dispersion resin or composite aqueous dispersion resin predetermined amounts of colloidal silica and deionized water set in each of Examples and Comparative Examples were added to uniformly adjust the solid content to 20% by mass.
  • a metal surface treating agent stock solution was obtained.
  • Table 1 shows the specific raw material mixing conditions of each of Examples 1 to 6 and Comparative Examples 1 to 5 for the stock solution of the metal surface treatment agent.
  • Each of the above steel sheets was spray-degreased with a 2% solution of Surf Cleaner 53 (S-paint paint Alguri degreaser) at 60 ° C for 120 seconds, washed with water, dried, Apply the metal surface treatment agent of Example or Comparative Example using a bar coater # 3 so that the film thickness after drying becomes 1 ⁇ , and bake and dry until the steel plate reaches a temperature of 150 ° C. A film was formed, and a test plate for evaluating the conductivity, corrosion resistance, and solvent resistance described below was obtained.
  • Surf Cleaner 53 S-paint paint Alguri degreaser
  • the above test material was further coated with Super Luck 100 (Melamine Alkyd Co., Ltd. made by Nippon Int. Co., Ltd.) as a top coat using a bar coater # 32 so that the film thickness after drying was 20 m.
  • the coating was applied, baked and dried at 150 at 20 minutes to form a coating film, and a test plate for evaluating the overcoat adhesion described later was obtained.
  • the evaluation method was based on the following methods.
  • the conductivity of the coating was evaluated by measuring the surface resistance (unit: ⁇ ) of the test material using Loresta (Mitsubishi Chemical surface resistance measuring device). Therefore, the smaller the value, the better the conductivity.
  • the numerical values in Tables 2 to 5 used the average value of the 10 measured values.
  • the corrosion resistance of the film was evaluated by spraying 5% saline solution at 35 ° C with the end face and back face of the test material sealed, and evaluating the white area generation area rate after 240 hours out of 10 points. did.
  • the test part was a “plane part”, a “worked part” extruded to 7 mm by an Erichsen tester, and a test plate with a degreasing agent (surf cleaner 53, Nippon Paint Co., Ltd.).
  • Paint adhesion was evaluated by a secondary adhesion test.
  • test plate was immersed in boiling water for 30 minutes, and then the following three items were evaluated: grid, elixir, and grid + Eriksen.
  • the grid is formed in advance and then processed using an Ericssen 'tester so that the grid-formed part protrudes by 7 mm.
  • the same evaluation was performed as for the item.
  • the evaluation criteria for all three items are as follows.
  • the metal surface treatment agent to be used is a water-dispersed resin having a solid content of 5 to 30% by mass, An aqueous composition containing 0.1 to 10% by mass, 0.02 to 5% by mass of a thiocarbonyl group-containing compound and 0.01 to 0.5% by mass of ion phosphate.
  • An aqueous dispersion obtained by reacting with an epoxy compound, ensuring corrosion resistance, excellent film conductivity, and excellent coating adhesion when a top coat is formed on the film. Can get 18 Yes.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Paints Or Removers (AREA)

Abstract

Metal surface-treatment agents, a metal surface-treatment method and surface-treated metal materials which are excellent in the film corrosion resistance and electric conductivity and coating adhesiveness in case of forming an over-coating layer on a film. Aqueous coatings for metal materials are aqueous compositions containing from 5 to 30 % by mass, on the solid basis, of an aqueous dispersion resin, from 1 to 10 % by mass of fine silica particles, from 0.02 to 5 % by mass of a thiocarbonyl-containing compound and from 0.01 to 0.5 % by mass of phosphate ion. The above-described aqueous dispersion resin is obtained by neutralizing 30 % or more of carboxyl groups containing from 10 to 30 % by mass of the unsaturated carboxylic acid with the use of potassium ion and then reacting the ionomer resin having been thus converted into an aqueous dispersion with an epoxy compound.
PCT/JP2002/001214 2001-02-14 2002-02-14 Metal surface-treatment agents, metal surface-treatment method and surface-treated metal materials WO2002064856A1 (fr)

Applications Claiming Priority (2)

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JP2001037605A JP2002241957A (ja) 2001-02-14 2001-02-14 金属表面処理剤、金属表面処理方法および表面処理金属材料
JP2001-37605 2001-02-14

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* Cited by examiner, † Cited by third party
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WO2005021638A3 (fr) * 2003-08-25 2005-05-26 Dow Global Technologies Inc Dispersion aqueuse, son procede de production et son utilisation
WO2005085331A1 (fr) 2004-02-27 2005-09-15 Dow Global Technologies Inc. Dispersions polymeres aqueuses et produits issus de ces dispersions
US7947776B2 (en) 2003-08-25 2011-05-24 Dow Global Technologies Llc Aqueous dispersion, its production method, and its use
US7981954B2 (en) 2005-01-28 2011-07-19 Basf Aktiengesellschaft Anti-corrosion coatings containing thioamide groups
AU2008201547B2 (en) * 2003-08-25 2012-01-19 Dow Global Technologies Llc Aqueous dispersion, its production method, and its use
US8618210B2 (en) 2003-08-25 2013-12-31 Dow Global Technologies, Llc Aqueous polymer dispersions and products from those dispersions
US8946329B2 (en) 2003-08-25 2015-02-03 Dow Global Technologies Llc Coating compositions
US9169406B2 (en) 2003-08-25 2015-10-27 Dow Global Technologies Llc Coating compositions
US9422444B2 (en) 2012-12-28 2016-08-23 Dow Global Technologies Llc Coating compositions
US9938413B2 (en) 2012-12-28 2018-04-10 Dow Global Technologies Llc Coating composition and articles made therefrom
EP3971174A4 (fr) * 2019-06-17 2023-08-09 Chemical Denshi Co., Ltd. Agent de traitement de surface métallique hydrophile

Families Citing this family (4)

* Cited by examiner, † Cited by third party
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KR101278867B1 (ko) 2005-01-28 2013-07-02 바스프 에스이 티오아미드를 포함하는 부식 보호층을 금속 표면에도포하는 방법
JP4598724B2 (ja) * 2005-06-30 2010-12-15 新日本製鐵株式会社 表面処理金属材
US20090215937A1 (en) * 2006-03-07 2009-08-27 Toho Chemical Industry Co., Ltd. Aqueous Resin Composition
JP5292962B2 (ja) * 2008-07-15 2013-09-18 Ｊｆｅスチール株式会社 表面処理鋼板及びその製造方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5381530A (en) * 1976-11-19 1978-07-19 Toray Ind Inc Resin composition for coating metal
JPS54138054A (en) * 1978-04-18 1979-10-26 Toray Ind Inc Resin composition for metal coating
JPH04314748A (ja) * 1991-01-17 1992-11-05 Du Pont Mitsui Polychem Co Ltd 水性分散体組成物及びそれを用いた硬化被膜ならびにその製法
JPH07331160A (ja) * 1994-06-03 1995-12-19 Nippon Parkerizing Co Ltd 亜鉛および／又はアルミニウム含有金属めっき鋼板用表面処理組成物、処理液および処理方法
WO1998059003A1 (fr) * 1997-06-20 1998-12-30 Mitsui Chemicals, Inc. Composition de dispersion aqueuse, son procede de preparation, antirouille et procede de prevention de la rouille et produits metalliques ainsi obtenus

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5381530A (en) * 1976-11-19 1978-07-19 Toray Ind Inc Resin composition for coating metal
JPS54138054A (en) * 1978-04-18 1979-10-26 Toray Ind Inc Resin composition for metal coating
JPH04314748A (ja) * 1991-01-17 1992-11-05 Du Pont Mitsui Polychem Co Ltd 水性分散体組成物及びそれを用いた硬化被膜ならびにその製法
JPH07331160A (ja) * 1994-06-03 1995-12-19 Nippon Parkerizing Co Ltd 亜鉛および／又はアルミニウム含有金属めっき鋼板用表面処理組成物、処理液および処理方法
WO1998059003A1 (fr) * 1997-06-20 1998-12-30 Mitsui Chemicals, Inc. Composition de dispersion aqueuse, son procede de preparation, antirouille et procede de prevention de la rouille et produits metalliques ainsi obtenus

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* Cited by examiner, † Cited by third party
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AU2008201547B2 (en) * 2003-08-25 2012-01-19 Dow Global Technologies Llc Aqueous dispersion, its production method, and its use
WO2005021638A3 (fr) * 2003-08-25 2005-05-26 Dow Global Technologies Inc Dispersion aqueuse, son procede de production et son utilisation
EP2264098A1 (fr) * 2003-08-25 2010-12-22 Dow Global Technologies Inc. Procédé de production d'une dispersion aqueuse
EP2272910A1 (fr) * 2003-08-25 2011-01-12 Dow Global Technologies Inc. Dispersion aqueuse
US7947776B2 (en) 2003-08-25 2011-05-24 Dow Global Technologies Llc Aqueous dispersion, its production method, and its use
US8946329B2 (en) 2003-08-25 2015-02-03 Dow Global Technologies Llc Coating compositions
US9169406B2 (en) 2003-08-25 2015-10-27 Dow Global Technologies Llc Coating compositions
US8618210B2 (en) 2003-08-25 2013-12-31 Dow Global Technologies, Llc Aqueous polymer dispersions and products from those dispersions
US9416291B2 (en) 2003-08-25 2016-08-16 Dow Global Technologies Llc Coating compositions
WO2005085331A1 (fr) 2004-02-27 2005-09-15 Dow Global Technologies Inc. Dispersions polymeres aqueuses et produits issus de ces dispersions
US7981954B2 (en) 2005-01-28 2011-07-19 Basf Aktiengesellschaft Anti-corrosion coatings containing thioamide groups
US9422444B2 (en) 2012-12-28 2016-08-23 Dow Global Technologies Llc Coating compositions
US9938413B2 (en) 2012-12-28 2018-04-10 Dow Global Technologies Llc Coating composition and articles made therefrom
EP3971174A4 (fr) * 2019-06-17 2023-08-09 Chemical Denshi Co., Ltd. Agent de traitement de surface métallique hydrophile

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