WO2008015968A1 - Agent de régulation de la conductivité pour un matériau de revêtement par électrodéposition cationique et procédé de régulation de la conductivité électrique d'un matériau de revêtement par électrodéposition cationique l'utilisant - Google Patents

Agent de régulation de la conductivité pour un matériau de revêtement par électrodéposition cationique et procédé de régulation de la conductivité électrique d'un matériau de revêtement par électrodéposition cationique l'utilisant Download PDF

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Publication number
WO2008015968A1
WO2008015968A1 PCT/JP2007/064743 JP2007064743W WO2008015968A1 WO 2008015968 A1 WO2008015968 A1 WO 2008015968A1 JP 2007064743 W JP2007064743 W JP 2007064743W WO 2008015968 A1 WO2008015968 A1 WO 2008015968A1
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WIPO (PCT)
Prior art keywords
cationic electrodeposition
conductivity
solid content
control agent
electrodeposition coating
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PCT/JP2007/064743
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English (en)
Japanese (ja)
Inventor
Satoru Uchidoi
Takefumi Yamamoto
Original Assignee
Nippon Paint Co., Ltd.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nippon Paint Co., Ltd. filed Critical Nippon Paint Co., Ltd.
Priority to US12/309,809 priority Critical patent/US20090321270A1/en
Priority to GB0901963A priority patent/GB2454123A/en
Priority to AU2007279812A priority patent/AU2007279812A1/en
Publication of WO2008015968A1 publication Critical patent/WO2008015968A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • 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
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/4488—Cathodic paints
    • C09D5/4492—Cathodic paints containing special additives, e.g. grinding agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • C08G59/08—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols from phenol-aldehyde condensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09D201/025—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing nitrogen atoms
    • 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
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/04—Electrophoretic coating characterised by the process with organic material
    • C25D13/06—Electrophoretic coating characterised by the process with organic material with polymers

Definitions

  • the present invention relates to a conductivity control agent for a cationic electrodeposition coating and adjustment of the electric conductivity of a cationic electrodeposition coating using the same.
  • Cationic electrodeposition coating is capable of applying even fine details even to an object having a complicated shape, and can be applied automatically and continuously. It is widely used as a method for undercoating undercoating with large and complex shapes. Cationic electrodeposition coating is performed by immersing an object to be coated in a cationic electrodeposition coating material as a cathode and applying a voltage.
  • cationic electrodeposition paints are water-based paint compositions having a solid content concentration of about 20% by weight, and when left without stirring, pigments and the like precipitate and precipitates are formed in the electrodeposition bath. Normally, cationic electrodeposition paints are circulated with a pump or stirred with a stirrer to prevent precipitation.
  • the cationic electrodeposition bath is a large-scale force that can immerse the car body, it is a powerful facility that can circulate and agitate, the energy involved, the equipment involved, and the power to maintain the equipment, and the cost involved. Will be enormous. Reducing or eliminating such circulation and agitation greatly contributes to energy saving in cationic electrodeposition coating. Therefore, it is effective that the cationic electrodeposition coating does not produce a precipitate or has a small amount of sediment. Specifically, it is effective to use a cationic electrodeposition coating having a low solid content or a low ash content. For the first time, electrodeposition paints are being studied!
  • Patent Document 1 discloses a cationic electrodeposition paint having a ash content of 3 to 10% by weight and a solid content concentration of 5 to 12% by weight. There is a disclosure of an environmentally-friendly electrodeposition coating method using paint. This cationic electrodeposition paint is excellent in that it has less sediment and power for agitation and circulation and less energy costs. S, in fact, as the solid content of the paint decreases, the electrical conductivity decreases, V. The performance of forming a coating film to every corner of the film will deteriorate.
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2004-269627
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2004-269627
  • This cationic electrodeposition coating composition contains a sulfone-modified epoxy resin and requires control of film resistance.
  • Patent Document 3 The amine value of the base resin of the cationic electrodeposition coating is being studied, such as JP-A-2005-232397 (Patent Document 3) and JP-A-7-150079 (Patent Document 4).
  • the amine value of urethane resin (substrate resin) is preferably 20 to 60 mgK OH / g (35.7-107.0 mmol / 100 g in terms of conversion), and the cationic electrodeposition property of Patent Document 4
  • the resin is described as having a desirable amine value of 3 to 200 mg KOH / g (in terms of conversion, 5.3-356 mmol / 100 g). These are the conventional ammine values, which are basically low.
  • Patent Document 1 Japanese Unexamined Patent Application Publication No. 2004_231989
  • Patent Document 2 JP 2004-269627 Koyuki
  • Patent Document 3 Japanese Unexamined Patent Publication No. 2005-232397
  • Patent Document 4 Japanese Patent Laid-Open No. 7-150079
  • the cationic electrodeposition coating composition having a low solid content and / or low ash content tends to have a lower electrical conductivity than a normal cationic electrodeposition coating composition.
  • the present invention provides a technique for preventing a decrease in throwing power accompanying a decrease in conductivity in a cationic solid electrodeposition coating composition having a low solid content and / or a low ash content.
  • the present invention is a conductivity control agent for a cationic electrodeposition paint used for a low solid content type cationic electrodeposition paint having a paint solid content concentration of 0.5 to 9.0 wt%, Molecular weight 50 Conductivity for cationic electrodeposition paints containing an amino group-containing compound with an amine value of 200-500 mmol / 100 g and adjusting the electric conductivity to 900-2,000 S / cm. Provide a degree control agent.
  • This conductivity control agent exists in cationic electrocoating paints as a separate emulsion from the cationic epoxy resin, curing agent and pigment, which is a film-forming component, and is actually formulated as the third component. To do.
  • the amino-containing compound used as the conductivity control agent is an amine-modified epoxy resin, and is preferably obtained by modifying an epoxy group contained in the epoxy resin with an amine compound.
  • the amino group-containing compound is also preferably an amine-modified acrylic resin obtained by modifying an epoxy group of an acrylic resin having an epoxy group with an amine compound.
  • the epoxy resin may be a bisphenol type, a t-butylcatechol type, a phenol novolac type, or a cresol nopolac type, and may have a number average molecular weight of 500 to 20,000.
  • the present invention is also a low solid content type cationic electrodeposition paint having a paint solid content concentration of 0.5 to 9.0% by weight and containing an amino group having an amine value of 200 to 500mmol / 100g.
  • a low solid content type cationic electrodeposition coating comprising a conductivity control agent containing a compound and having an electrical conductivity of 900 to 2,000 S / cm.
  • the present invention further relates to a method for adjusting the electrical conductivity of a cationic electrodeposition coating material, comprising a low solid content type cationic electrodeposition coating material having a coating solid content concentration of 0.5 to 9.0% by weight. Adding a conductivity control agent;
  • the conductivity control agent comprises an amino group-containing compound having an amine value of 200 to 500 mmol / 100 g.
  • the present invention is also a method for supplying a conductivity control agent to a cationic electrodeposition paint.
  • the conductivity control agent comprises an amino group-containing compound having an amine value of 200 to 500 mmol / 100 g.
  • the disadvantage of the low ash type and / or low solid content type cationic electrodeposition paint is achieved. This is to eliminate the decrease in throwing power that accompanies the decrease in conductivity of a cationic electrodeposition paint.
  • FIG. 1 is a perspective view showing an example of a box used for evaluating throwing power.
  • FIG. 2 is a cross-sectional view schematically showing a throwing power evaluation method.
  • the conductivity control agent for cationic electrodeposition paints of the present invention is composed of an amino group-containing compound having an amine value of 200 to 500 mmol / 100 g.
  • the conductivity control agent for cationic electrodeposition coating of the present invention may be any amino group-containing compound as long as the amine value has the above range, but usually an amine-modified epoxy resin or an amine-modified acrylic resin is preferred. .
  • the conductivity control agent for cationic electrodeposition paints of the present invention may be neutralized with an acid, if necessary.
  • the amine value is preferably 250 to 450 mmol / 100 g, and most preferably 300 to 400 mmol / 100 g.
  • the amine value is 200 mmol / 100 g / J or more, the amount required to adjust the liquid conductivity of the low solid content cationic electrodeposition paint to the optimum value increases, which may impair the corrosion resistance. On the other hand, if it exceeds 500 mmol / 100 g, the precipitation property is lowered and the desired throwing power cannot be obtained. In addition, the suitability of galvanized steel sheets is also reduced.
  • the amino group-containing compound as the conductivity control agent for cationic electrodeposition coatings in the present invention can be considered to have a low molecular weight to a high molecular weight ordinary amine-modified epoxy resin diamine-modified acrylic resin, etc. And high molecular weight compounds.
  • the low molecular weight amino group-containing compound include monoethanolamine, diethanolamine, and dimethylbutylamine.
  • Epoxy resins that can be used in general include bisphenol type epoxy resin, t-butylcatechol type epoxy resin, phenol nopolac type epoxy resin, and cresol nopolac type epoxy resin, having a molecular weight of 500 to 20000. Those having the following are preferred. Of these epoxy resins, phenol nopolac type epoxy resins and cresol nopolac type epoxy resins are most desirable. In particular, these epoxy resins are commercially available. Examples thereof include phenolic nopolak type epoxy resin DEN-438 manufactured by Dow Chemical Japan, and cresol nopolac type epoxy resin YDCN-703 manufactured by Tohto Kasei Co., Ltd.
  • epoxy resins may be modified with resins such as polyester polyols, polyether polyols, and monofunctional alkylphenols. Epoxy resins can also be chain-extended using the reaction of epoxy groups with diols or dicarboxylic acids.
  • amine-modified acrylic resin for example, a homopolymer of dimethylaminoethyl methacrylate which is an amino group-containing monomer or a copolymer with another polymerizable monomer is used as it is. Alternatively, it may be used by modifying the glycidyl group of a homopolymer of glycidyl metatalylate or a copolymer with other polymerizable monomer with an amine compound.
  • Examples of the compound that introduces an amino group into an epoxy resin or an acrylic resin containing an epoxy group include primary amines, secondary amines, and tertiary amines. Specific examples thereof include butynoreamine, talented cutinoleamine, jetinoreamine, dibutinoreamine, dimethylenobutyneamine, monoethanolamine, diethanolamine, N-methylethanolamine, triethylamine hydrochloride, N, N-dimethylethanolamine.
  • primary amine-blocked secondary amines such as aminoethylethanolamine diketimine, jetylhydroamine diketimine and the like can be mentioned.
  • a plurality of amines may be used.
  • the number average molecular weight of these amine-modified epoxy resins and amine-modified acrylic resins is preferably 500 to 20000. If the number average molecular weight is less than 500, corrosion resistance may be impaired, and although the reason is not clear, a decrease in throwing power and a decrease in suitability for galvanized steel sheets are observed. If the number average molecular weight is greater than 20000 !, there is a risk of causing a decrease in the finished appearance.
  • the cationic electrodeposition paint to which the conductivity control agent for cationic electrodeposition paint of the present invention can be applied is not limited to a low solid content type cationic electrodeposition paint having a solid content concentration of 0.5 to 9.0% by weight. It is also possible to apply to a normal cationic electrodeposition paint having a solid content concentration of about 20% by weight. Even with normal cationic electrodeposition paints, the electrical conductivity may be reduced, and if the electrodeposition is applied as it is, the throwing power may be insufficient. When such a problem occurs, the conductivity can be controlled to an appropriate value by adding the above-mentioned conductivity control agent for cationic electrodeposition paints to normal cationic electrodeposition paints. Therefore, sufficient throwing power can be secured.
  • Acids used for neutralization are inorganic acids or organic acids such as hydrochloric acid, nitric acid, phosphoric acid, sulfamic acid, formic acid, acetic acid, and lactic acid.
  • the conductivity control agent for cationic electrodeposition paints according to the present invention has a compounding amount in cationic electrodeposition paints. By adjusting, the electric conductivity of the electrodeposition coating material can be suitably adjusted.
  • Cationic electrodeposition coating compositions include those containing a cationic epoxy resin, a curing agent, and optionally pigments and additives. Hereinafter, each component will be described.
  • the cationic epoxy resin used in the present invention includes an epoxy resin modified with amine.
  • Cationic epoxy resins typically have the ability to open with active hydrogen compounds that can introduce cationic groups into all of the epoxy rings of bisphenol type epoxy resins, or some epoxy rings to other It is produced by opening a ring with an active hydrogen compound and opening the remaining epoxy ring with an active hydrogen compound capable of introducing a cationic group.
  • Power of cationic electrodeposition paint Thion-based epoxy resin preferably has an amine value of 50 to 200 mmol / 100 g, which is smaller than the amine value (200 to 500 mmol / 100 g) of the conductivity control agent for cationic electrodeposition paint. It has a great value.
  • the amine value is less than 50 mmol / 100 g, the dispersibility of the cation-modified epoxy resin in water cannot be ensured, and if it exceeds 200 mmol / 100 g, the water resistance of the resulting coating film may be deteriorated.
  • a typical example of the bisphenol type epoxy resin is a bisphenol A type or bisphenol F type epoxy resin.
  • Epicoat 828 manufactured by Yuka Shell Epoxy Co., Epoxy Equivalent 180 ⁇ ; 190
  • Epico 1001 Equivalent Epoxy Equivalent 450 ⁇ 500
  • Epicote 1010 Equipment Equivalent Equivalent 3000 ⁇ 4000
  • Epicoat 807 epoxy equivalent 170
  • R represents a residue excluding the glycidyloxy group of the diglycidyl epoxy compound
  • R ′ represents an isocyanato group of the diisocyanate compound
  • n represents a positive integer.
  • a block polyisocyanate blocked with a lower alcohol such as methanol and a polyepoxide are heated and kept in the presence of a basic catalyst to produce a by-product lower product. Obtained by distilling off alcohol from the system.
  • epoxy resins may be modified with an appropriate resin such as polyester polyol, polyether polyol, and monofunctional alkylphenol. Epoxy resins also have the ability to extend the chain using the reaction of epoxy groups with diols or dicarboxylic acids.
  • epoxy resins are ring-opened with an active hydrogen compound so that an amine value of 50 to 200 mmol / 100 g is obtained after ring opening, and more preferably 5 to 50% of them are occupied by primary amino groups. Is desirable.
  • the active hydrogen compounds capable of introducing a cationic group include primary amines, secondary amines, tertiary amine acid salts, sulfides and acid mixtures.
  • primary amine, secondary amine, or tertiary amine acid salts are used as active hydrogen compounds capable of introducing cationic groups.
  • Specific examples include butylamine, octylamine, jetylamine, dibutylamine, methylbutyramine, monoethanolamine, diethanolamine, N-methylethanolamine, triethylamine hydrochloride, N, N-dimethylethanolamine acetate, jetyl disulfide.
  • a secondary amine that blocks primary amines, such as a mixture of acetic acid, ketimine of aminoethylethanolamine, diketimine of dimethyltriamine. Amines can be used in combination.
  • the curing agent used in the present invention is preferably a blocked polyisocyanate obtained by blocking a polyisocyanate with a blocking agent.
  • a polyisocyanate means two isocyanate groups in one molecule.
  • the polyisocyanate may be, for example, any of aliphatic, alicyclic, aromatic and aromatic aliphatic.
  • Specific examples of polyisocyanates include aromatic diisocyanates such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), p-phenylene diisocyanate, and naphthalene diisocyanate.
  • aliphatic diisocyanates such as hexamethylene diisocyanate (HDI), 2, 2, 4 trimethylhexane diisocyanate, lysine diisocyanate and the like; Hexane diisocyanate (CDI), isophorone diisocyanate (IPDI), 4,4'-dicyclohexylenomethane diisocyanate (hydrogenated MDI), methylcyclohexane diisocyanate, isopropylidenedicyclohexane Hexolux 4,4'-diisocyanate and 1,3-diisocyanatomethylcyclohexane (hydrogenated XDI), hydrogenated TDI, 2, 5 or 2, 6 C5-C18 alicyclic diisocyanates such as bis (isocyanatomethyl) monobicyclo [2.2.1] heptane (also called norbornane diisocyanate); xylylene diisocyanate (XDI), X
  • Adducts or prepolymers obtained by reacting polyisocyanate with polyhydric alcohols such as ethylene glycol, propylene glycol, trimethylolpropan and hexanetriol at an NCO / OH ratio of 2 or more are also used as curing agents. It's okay.
  • the polyisocyanate is preferably an aliphatic polyisocyanate or an alicyclic polyisocyanate! /. This is because the formed coating film is excellent in weather resistance.
  • aliphatic polyisocyanate or alicyclic polyisocyanate include hexamethylene diisocyanate, hydrogenated TDI, hydrogenated MDI, hydrogenated XDI, IPDI, norbornane diisocyanate, and the like. Dimer (biuret), trimer (isocyanurate) and the like.
  • the blocking agent is added to a polyisocyanate group and is stable at room temperature, but can regenerate a free isocyanate group when heated to a temperature higher than the dissociation temperature.
  • a blocking agent when low-temperature curing (160 ° C or less) is desired, ratata series such as ⁇ -force prolatatam, ⁇ -noratalatata, ⁇ -butyroratam and / 3-propiolatata Blocking agents and formaldoxime, acetoaldoxime, acetoxime, methylethyl blocking agents may be used.
  • the binder containing the cationic epoxy resin and the curing agent is generally an electrodeposition coating composition in an amount of 25 to 85% by weight, preferably 40 to 70% by weight of the total solid content of the electrodeposition coating composition. Contained in
  • the electrodeposition coating composition used in the present invention may contain a commonly used pigment.
  • pigments that can be used include commonly used inorganic pigments, such as colored pigments such as titanium white, carbon black and bengara; kaolin, talc, aluminum silicate, calcium carbonate, my strength and clay.
  • Extender pigments zinc phosphate, iron phosphate, ammonium phosphate, calcium phosphate, zinc phosphite, zinc cyanide, zinc oxide, aluminum tripolyphosphate, zinc molybdate, aluminum molybdate, calcium molybdate and phosphomolybdic acid
  • anti-mold pigments such as aluminum, aluminum zinc phosphomolybdate, bismuth hydroxide, bismuth oxide, basic bismuth carbonate, bismuth nitrate, bismuth benzoate, bismuth citrate, and bismuth silicate.
  • the pigment is generally contained in the electrodeposition coating composition in an amount accounting for the total solid content of the electrodeposition coating composition;! To 35 wt%, preferably 10 to 30 wt%.
  • a pigment When a pigment is used as a component of an electrodeposition coating, it is generally dispersed in an aqueous medium at a high concentration in advance together with a resin called a pigment dispersion resin to make a paste. This is because it is difficult to disperse the pigment in a single step in a low concentration uniform state used in the electrodeposition coating composition because the pigment is in powder form. In general, such a paste is referred to as a pigment dispersion paste.
  • the pigment dispersion paste is prepared by dispersing a pigment together with a pigment dispersion resin varnish in an aqueous medium.
  • a pigment dispersion resin varnish a cationic polymer such as a cationic or nonionic low molecular weight surfactant or a modified epoxy resin having a quaternary ammonium group and / or a tertiary sulfone group is generally used. Is used.
  • As the aqueous medium ion-exchanged water or water containing a small amount of alcohol is used.
  • pigment dispersion resin varnish is 5-40 Part by weight and pigment are used at a solid content ratio of 10 to 30 parts by weight.
  • the cationic electrodeposition coating composition of the present invention needs to have a coating solid content concentration of 0.5 to 9.0% by weight.
  • a coating solid content concentration of paint is below the lower limit, a cationic electrodeposition coating film cannot be obtained.
  • the coating solid content concentration exceeds the upper limit, the pigment component contained in the cationic electrodeposition coating material settles in a stationary state without stirring, which is not preferable.
  • the electrodeposition coating composition is prepared by dispersing a cationic epoxy resin, a curing agent, and a pigment dispersion paste in an aqueous medium.
  • the aqueous medium contains a neutralizing agent in order to improve the dispersibility of the cationic epoxy resin.
  • Neutralizing agents are inorganic or organic acids such as hydrochloric acid, nitric acid, phosphoric acid, formic acid, acetic acid, lactic acid.
  • the amount is an amount that achieves a neutralization rate of at least 20%, preferably 30-60%.
  • the amount of the curing agent reacts with active hydrogen-containing functional groups such as primary, secondary or / and tertiary amino groups and hydroxyl groups in the cationic epoxy resin at the time of curing to give a good cured coating film.
  • active hydrogen-containing functional groups such as primary, secondary or / and tertiary amino groups and hydroxyl groups in the cationic epoxy resin at the time of curing to give a good cured coating film.
  • active hydrogen-containing functional groups such as primary, secondary or / and tertiary amino groups and hydroxyl groups in the cationic epoxy resin at the time of curing to give a good cured coating film.
  • active hydrogen-containing functional groups such as primary, secondary or / and tertiary amino groups and hydroxyl groups in the cationic epoxy resin at the time of curing to give a good cured coating film.
  • active hydrogen-containing functional groups such as primary, secondary or / and tertiary amino groups and hydroxyl groups in the cationic epoxy resin at the
  • the electrodeposition paint may contain a tin compound such as dibutyltin dilaurate and dibutyltin oxide, and a usual urethane cleavage catalyst. Since a lead-free material is preferable, the amount is preferably set to 0.;! To 5% by weight of the block polyisocyanate compound.
  • a tin compound such as dibutyltin dilaurate and dibutyltin oxide
  • a usual urethane cleavage catalyst Since a lead-free material is preferable, the amount is preferably set to 0.;! To 5% by weight of the block polyisocyanate compound.
  • the electrodeposition coating composition may contain conventional coating additives such as a water-miscible organic solvent, a surfactant, an antioxidant, an ultraviolet absorber, and a pigment.
  • the cationic electrodeposition coating composition of the present invention is not particularly limited as long as it contains the components described above, but the conductivity control agent for cationic electrodeposition coating of the present invention is effective.
  • the cationic electrodeposition coating used is of the low solids type.
  • the cationic electrodeposition paint of the present invention may be a low ash type.
  • the low solid content type cationic electrodeposition coating composition has a solid content concentration of less than the conventional 20% by weight, particularly 0.5 to 9% by weight, and a more preferred lower limit is 3% by weight. If it is less than 0.5% by weight, the pigment component settles without stirring, which is not preferable. On the other hand, although it may exceed 9% by weight, it may not be necessary to adjust the electrical conductivity of the paint by adding a conductivity modifier for cationic electrodeposition paints.
  • the cationic electrodeposition coating used in the present invention can be said to be a low ash type.
  • the ash content is 15 to 40% by weight in the case of an ordinary cathodic electrodeposition paint, so the ash content of the low ash type cationic electrodeposition paint is preferably 2 to 7% by weight, more preferably 3 to 5% by weight. is there.
  • the object to be coated when electrodeposition coating is performed using the electrodeposition coating composition is preferably a conductor that has been subjected to surface treatment such as zinc phosphate treatment in advance by dipping, spraying, or the like.
  • the surface treatment may not be performed.
  • the conductor is preferably a metal substrate that is not particularly limited as long as it can serve as a cathode in electrodeposition coating.
  • Electrodeposition Conditions under which electrodeposition is performed are generally the same as those used for other types of electrodeposition coating.
  • the applied voltage may vary greatly and may range from 1 to several hundred volts.
  • the current density is typically about 10 amps / m 2 to 160 amps / m 2 and tends to decrease during electrodeposition.
  • the coating is baked at an elevated temperature in a conventional manner, for example, in a baking furnace, in a baking oven or with an infrared heat lamp.
  • the baking temperature is usually about 140 ° C to 180 ° C.
  • the coated product coated with the cationic electrodeposition paint of the present invention is dried and baked after the final water washing to form a cured electrodeposition coating film, thereby completing the coating process.
  • the above-described liquid conductivity control agent for cationic electrodeposition coating is used as a cationic electrodeposition coating.
  • the liquid conductivity of the paint is ensured.
  • low solid content type cationic electrodeposition coatings tend to have insufficient liquid conductivity compared to ordinary cationic electrodeposition coatings with a solid content concentration of about 20% by weight.
  • Adjust by adding a specific conductivity control agent for cationic electrodeposition coatings By increasing the amine value of the cation-modified epoxy resin as a coating film forming component, it is possible to maintain electric conductivity at an appropriate value and to ensure throwing power.
  • the electric conductivity necessary for obtaining the desired throwing power is 900 to 2000 S / cm.
  • the conductivity control agent for the cationic electrodeposition paint of the present invention the low solid content type electrodeposition paint
  • the liquid conductivity of can be controlled within this range.
  • the preferred lower limit of conductivity is 1000 3 /.
  • the preferred upper limit is 1800 S / cm. If the electrical conductivity is less than 900 a S / cm, the desired throwing power cannot be obtained.
  • conductivity is more than 2000 ⁇ S / cm, coating defects called gas pins are likely to occur when coating galvanized steel sheets. Have the following disadvantages. Conductivity is measured using a commercially available liquid conductivity meter at a liquid temperature of 25 ° C.
  • the blending amount of the conductivity control agent for the cationic electrodeposition coating material in the cationic electrodeposition coating material is not particularly limited as long as a predetermined electric conductivity is obtained. Specifically, it is based on the solid content of the coating material. There are, from 0.5 to 30 weight 0/0, preferably 1 to 30 weight 0/0, more preferably 1 to; Ru 15 weight% der. Although it may be less than 0.5% by weight, sufficient electrical conductivity may not be obtained. The blending amount may exceed 50% by weight, but no increase in electrical conductivity proportional to the amount added will be observed.
  • the low solid content type cationic electrodeposition coating material having the conductivity adjusted as described above is a low ash content and low solid content type cationic electrodeposition coating material, and can ensure suitable throwing power. Even for such cationic electrodeposition paints, it is necessary to replenish the film-forming components in the cationic electrodeposition paint tank in the process of repeatedly coating the object to be coated on the painting line. At this time, the electrical conductivity of the cationic electrodeposition paint in the tank may deviate from the range of 900 to 2,000 S / cm desired by the present application. When the electrical conductivity is 900 S / cm or less, the conductivity adjustment agent of the present invention is separately added to the cationic electrodeposition coating tank to reduce the solid content concentration to 0. The electric conductivity of the cationic electrodeposition paint in the tank can be adjusted to the range of 900 to 2,000 a S / cm while maintaining the content at 5 to 9.0% by weight.
  • MIBK methylisoptyl ketone
  • methinorethananolamine 37.5 parts
  • diethanolamine 52.5 parts
  • MIBK methylisoptyl ketone
  • Example A-1 To 140 parts of the amino modified resin solution obtained in Example A-1, 5.5 parts of formic acid and 54.5 parts of deionized water 12 are added and stirred for 30 minutes while maintaining at 80 ° C. The organic solvent was removed under reduced pressure to obtain a liquid conductivity control agent A having a solid content of 7.0%.
  • a flask equipped with a reflux condenser and a stirrer is charged with 255 parts of MIBK and 75 parts of methylethanolamine and kept at 100 ° C. while stirring. To this, gradually add 180 parts of phenol nopolak type epoxy resin (trade name DEN-438, manufactured by Dow Chemical Japan Co., Ltd.). The molecular weight was measured and found to be 1,000. The amine value (MEQ (B)) of the obtained amino-modified resin was measured and found to be 390 mmol / 100 g.
  • Example C 1 To 140 parts of the amino-modified resin solution obtained in Example B-1, 14 parts of sulfamic acid and 1247 parts of deionized water are added and stirred for 30 minutes while maintaining the temperature at 80 ° C. The organic solvent was removed under reduced pressure to obtain a liquid conductivity control agent B having a solid content of 7.0%. [0072]
  • Example C 1 To 140 parts of the amino-modified resin solution obtained in Example B-1, 14 parts of sulfamic acid and 1247 parts of deionized water are added and stirred for 30 minutes while maintaining the temperature at 80 ° C. The organic solvent was removed under reduced pressure to obtain a liquid conductivity control agent B having a solid content of 7.0%.
  • MIBK methyl isobutyl ketone
  • a mixed solution consisting of 100 parts of glycidino methacrylate and 2 parts of azobisisobutyronitrile (AIBN) was added dropwise at a constant rate from a dropping funnel in 2 hours. The temperature was kept at 100 ° C and stirring was continued for 30 minutes. Thereafter, a mixture of 52.5 parts of MIBK and 0.5 part of AIBN was added dropwise over 1 hour. Stirring was continued for another hour to complete the reaction.
  • MIBK methyl isobutyl ketone
  • Example C-1 A flask equipped with a reflux condenser and a stirrer is charged with 57.5 parts of MIBK and 52.8 parts of methylethanolamine and kept at 100 ° C while stirring. To this, 205 parts of the reaction product obtained in Example C-1 is gradually added, and after the entire amount has been added, the reaction is allowed to proceed for 3 hours. The molecular weight was measured and found to be 9,800. The amine value (MEQ (B)) of the obtained amino-modified resin was measured and found to be 450 mmol / 100 g.
  • Example C-2 To 140 parts of the amino modified resin solution obtained in Example C-2, 25.2 parts of lactic acid and 1234.8 parts of deionized water are added and stirred for 30 minutes while maintaining at 80 ° C. The organic solvent was removed under reduced pressure to obtain a liquid conductivity control agent C having a solid content of 7.0%.
  • Liquid conductivity regulator with an active ingredient's amine value (MEQ (B)) of 740 mmol / 100 g and an active ingredient concentration of 7%
  • a flask equipped with a stirrer, condenser, nitrogen inlet tube, thermometer and dropping funnel was charged with 95 parts and dibutyltin dilaurate 0.5 parts. While stirring the reaction mixture, 21 parts of methanol was added dropwise. The reaction starts at room temperature and is 60 ° C due to exotherm. The temperature was raised to. Thereafter, the reaction was continued for 30 minutes, and then 50 parts of ethylene glycol mono-2-ethylhexyl ether was added dropwise from the dropping funnel. Further, 53 parts of a bisphenol A-propylene oxide 5 mol adduct was added to the reaction mixture. The reaction was mainly carried out in the range of 60 to 65 ° C. and continued until the absorption based on the isocyanate group disappeared in the IR spectrum measurement.
  • a reactor was charged with 1250 parts of diphenylmethane diisocyanate and 4 parts of MIBK266. This was heated to 80 ° C, and 2.5 parts of dibutyltin dilaurate was added. Here, 226 parts of epsilon prolatatum were dissolved in 944 parts of butylcetone sorb, and dropped at 80 ° C. over 2 hours. After further heating at 100 ° C for 4 hours, in the IR spectrum measurement, it was confirmed that the absorption based on the isocyanate group disappeared, and after cooling, 1 part MIBK336.1 was added to block the glass transition temperature at 0 ° C. An isocyanate curing agent was obtained.
  • IPDI isophorone diisocyanate
  • EPON 829 (Bisphenol A type epoxy epoxies, ephemeral equivalent of 193-203, manufactured by Shell 'Chemical' Company) 71.0. And bisphenol A289.6 ⁇ are appropriate.
  • the reaction mixture was allowed to react at 150-; 160 ° C for about 1 hour, then cooled to 120 ° C, and then 498.8 parts of 2-ethylhexanol half-blocked IPDI (MIBK solution) prepared previously was I got it.
  • reaction mixture was kept at 110-120 ° C for about 1 hour, then 463.4 parts of ethylene glycol monobutyl ether was added, the mixture was cooled to 85-95 ° C, homogenized, and then first. 196. 7 parts of the prepared quaternizing agent was added. After maintaining the reaction mixture at 85 to 95 ° C until the acid value becomes 1, add 964 parts of deionized water to finish quaternization in epoxy bisphenol A resin, and a pigment having a quaternary ammonium salt part A resin for dispersion was obtained (resin solid content 50%).
  • the amine-modified epoxy resin obtained in Production Example 11 and the block isocyanate curing agent obtained in Production Example 12 were mixed so as to be uniform at a solid content ratio of 80/20. Glacial acetic acid was added to this so that the milligram equivalent (MEQ (A)) of the acid per 100 g of resin solid content was 30, and ion-exchanged water was slowly added to dilute. Removal of MIBK under reduced pressure yielded an emulsion with a solid content of 36%.
  • MEQ (A) milligram equivalent
  • an electrodeposition coating composition F having a solid content of 20%.
  • the concentration of the pigment contained in the solid content of the cationic electrodeposition coating composition was 23% by weight.
  • the solid content of the paint can be determined as a percentage of the original mass of the mass of the residue after heating at 180 ° C for 30 minutes. (Conforms to JIS K5601)
  • the electrodeposition coating composition F obtained here was used as Comparative Example 1 as it was.
  • the liquid conductivity was 1600 S / cm.
  • Example 1 By adding 6 parts of the liquid conductivity control agent A obtained in Example A-2 to 1000 parts of the previously obtained electrodeposition coating composition G, the liquid conductivity was reduced to 1200 S / cm. An adjusted electrodeposition coating composition H was obtained. This electrodeposition coating composition H was used as Example 1.
  • Example 2 By adding 8 parts of the liquid conductivity control agent B obtained in Example B-2 to 1000 parts of the previously obtained electrodeposition coating composition G, the liquid conductivity was reduced to 1300 S / cm. An adjusted electrodeposition coating composition I was obtained. This electrodeposition coating composition I was used as Example 2.
  • the liquid conductivity was adjusted to 1100 S / cm by adding 3 parts of the liquid conductivity control agent C obtained in Example C 3 to 1000 parts of the previously obtained electrodeposition coating composition G.
  • An electrodeposition coating composition J was obtained. This electrodeposition coating composition J was used as Example 3.
  • the solid content concentration was reduced from 7% to 5% by adding 400 parts of ion exchange water to 1000 parts of the electrodeposition coating composition G obtained previously. This operation decreased the liquid conductivity from 890 a S / cm to 640 S / cm.
  • the liquid conductivity control obtained in Example A-2 was used.
  • An electrodeposition coating composition K having a liquid conductivity adjusted to 1100 S / cm was obtained by adding 8 parts of control agent A. This electrodeposition coating composition K was used as Example 4.
  • the throwing power was evaluated by the so-called four-sheet box method. That is, as shown in Fig. 1, four zinc phosphate-treated steel plates (JIS G3141 SPCC—SD surfdyne SD-50 00 (manufactured by Nippon Paint)) 11 ⁇ ; Box 10 was prepared, which was placed in parallel at 20 mm, and the bottom and bottom surfaces of both sides were sealed with an insulating material such as cloth adhesive tape. In addition, the steel plates 11 to 13 other than the steel plate 14 are provided with through holes 15 of 8 mm ⁇ at the bottom.
  • JIS G3141 SPCC—SD surfdyne SD-50 00 manufactured by Nippon Paint
  • the coating material 21 was stirred with a magnetic stirrer (not shown).
  • the steel plates 11 to 14 were electrically connected, and the counter electrode 22 was arranged so that the distance between the steel plate 11 and the steel plate 11 was 150 mm.
  • Cathode electrodeposition coating was performed on steel rice with a voltage applied with each steel plate 11-; 14 as a cathode and the counter electrode 22 as an anode.
  • the pressure is increased to a voltage at which the film thickness of the coating film formed on the A side of steel plate 11 reaches 15 ⁇ in 5 seconds, and then for 175 seconds for normal electrodeposition and 115 seconds for short time electrodeposition. This was done by maintaining the voltage.
  • the alloyed hot-dip galvanized steel rice subjected to chemical conversion treatment was pressurized to 220V for 5 seconds, electrodeposited for 175 seconds, washed with water, baked at 170 ° C for 25 minutes, and the state of the coating film was observed. Applicable when no abnormalities are observed (Legend; A), slightly abnormalities are observed (Legend; B), markedly abnormal, when abnormalities are observed (Legend; C) It was judged.
  • the electrical conductivity of the cationic electrodeposition coating compositions obtained in Examples and Comparative Examples was measured using a conductivity meter (CM-305 manufactured by Toa Denpa Kogyo Co., Ltd.) at a liquid temperature of 25 ° C. .
  • Comparative Example 1 is normal This is a cationic electrodeposition paint with a solid content (20% by weight) of paint, and the liquid conductivity is in the range of the present invention.
  • Comparative Example 2 is a cationic electrodeposition paint having a low solid content concentration of 7% by weight, and the electroconductivity of the electrodeposition paint is insufficient, resulting in a decrease in rolling characteristics.

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Abstract

La présente invention concerne une technologie qui empêche la détérioration de la conductivité et du pouvoir couvrant dans une composition de matériau de revêtement par électrodéposition cationique à faible teneur en solides et en cendres. Elle concerne par exemple un agent de régulation de la conductivité pour un matériau de revêtement par électrodéposition cationique à utiliser dans un matériau de revêtement par électrodéposition cationique dont la faible teneur en solide est comprise entre 0,5 et 9,0 % en poids, comprenant un composé aminé dont le poids moléculaire est compris entre 500 et 20 000 et dont l'indice d'amine est compris entre 200 et 500 mmol/100 g pour permettre une régulation de la conductivité électrique entre 900 et 2000 µS/cm. L'invention concerne en outre un procédé de régulation de la conductivité électrique d'un matériau de revêtement par électrodéposition cationique, dont les étapes consistent à mélanger un agent de régulation de la conductivité avec un matériau de revêtement par électrodéposition cationique dont la faible teneur en solide est comprise entre 0,5 et 9,0 % en poids ; et à réguler la conductivité électrique du matériau de revêtement par électrodéposition cationique à faible teneur en solide après l'étape de mélange entre 900 et 2000 µS/cm. L'agent de régulation de la conductivité selon l'invention contient un composé aminé dont l'indice d'amine est compris entre 200 et 500 mmol/100 g.
PCT/JP2007/064743 2006-08-01 2007-07-27 Agent de régulation de la conductivité pour un matériau de revêtement par électrodéposition cationique et procédé de régulation de la conductivité électrique d'un matériau de revêtement par électrodéposition cationique l'utilisant WO2008015968A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US12/309,809 US20090321270A1 (en) 2006-08-01 2007-07-27 Electroconductivity-controlling agent for cationic electrodeposition coating composition and method for adjusting electroconductivity of cationic electrodeposition coating composition therewith
GB0901963A GB2454123A (en) 2006-08-01 2007-07-27 Conductivity control agent for cationic electrodeposition coating material and method of regulating electric conductivity of cationic electrodeposition
AU2007279812A AU2007279812A1 (en) 2006-08-01 2007-07-27 Conductivity control agent for cationic electrodeposition coating material and method of regulating electric conductivity of cationic electrodeposition coating material using the same

Applications Claiming Priority (2)

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JP2006-209954 2006-08-01
JP2006209954A JP2008037889A (ja) 2006-08-01 2006-08-01 カチオン電着塗料用電導度制御剤およびそれを用いるカチオン電着塗料の電気電導度調整方法

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JP5325658B2 (ja) * 2009-06-03 2013-10-23 日本ペイント株式会社 カチオン電着塗料の付き回り性の向上方法
CN102912400A (zh) * 2012-10-25 2013-02-06 奥捷五金(江苏)有限公司 不锈钢多色电泳涂装工艺
JP6406842B2 (ja) * 2014-03-25 2018-10-17 日本ペイント・オートモーティブコーティングス株式会社 電着塗料組成物および電着塗装方法
CN108717040A (zh) * 2018-05-31 2018-10-30 廊坊立邦涂料有限公司 一种在实验室模拟现场电泳漆泳透力的装置及模拟方法
CN111057408A (zh) * 2019-12-05 2020-04-24 广东科德环保科技股份有限公司 一种电泳涂料的阳离子型改性助剂及其制备方法

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JPH03188298A (ja) * 1989-12-14 1991-08-16 Kansai Paint Co Ltd 電着塗膜形成方法
JPH06346290A (ja) * 1993-06-11 1994-12-20 Kansai Paint Co Ltd 塗装方法
JP2003313495A (ja) * 2002-02-21 2003-11-06 Kansai Paint Co Ltd カチオン電着塗料組成物

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CA2128843C (fr) * 1993-07-30 1997-10-07 Susumu Midogohchi Composition pour revetement par electrodeposition
JP4035836B2 (ja) * 1995-09-26 2008-01-23 日本ペイント株式会社 艶消しカチオン電着塗料組成物
US6031028A (en) * 1996-07-12 2000-02-29 Kansai Paint Company, Limited Cationic electrodeposition coating composition
JP2002126618A (ja) * 2000-10-26 2002-05-08 Nippon Paint Co Ltd 多層塗膜形成方法及び多層塗膜
JP2002126640A (ja) * 2000-10-26 2002-05-08 Nippon Paint Co Ltd 塗膜形成方法及び塗膜並びに水性塗料組成物
JP2002129099A (ja) * 2000-10-26 2002-05-09 Nippon Paint Co Ltd カチオン電着塗料組成物およびこれを用いる多層塗膜形成方法
JP3817674B2 (ja) * 2003-01-28 2006-09-06 関西ペイント株式会社 環境対応型電着塗装方法及び塗装物品
JP4959114B2 (ja) * 2004-03-01 2012-06-20 日本ペイント株式会社 電着塗料組成物、電着浴の管理方法および電着塗装システム

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JPH03188298A (ja) * 1989-12-14 1991-08-16 Kansai Paint Co Ltd 電着塗膜形成方法
JPH06346290A (ja) * 1993-06-11 1994-12-20 Kansai Paint Co Ltd 塗装方法
JP2003313495A (ja) * 2002-02-21 2003-11-06 Kansai Paint Co Ltd カチオン電着塗料組成物

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