WO2012153850A1 - 狭いクリアランス部にまで塗装可能なカチオン電着塗料組成物及びそれを用いた電着塗膜形成方法 - Google Patents
狭いクリアランス部にまで塗装可能なカチオン電着塗料組成物及びそれを用いた電着塗膜形成方法 Download PDFInfo
- Publication number
- WO2012153850A1 WO2012153850A1 PCT/JP2012/062195 JP2012062195W WO2012153850A1 WO 2012153850 A1 WO2012153850 A1 WO 2012153850A1 JP 2012062195 W JP2012062195 W JP 2012062195W WO 2012153850 A1 WO2012153850 A1 WO 2012153850A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- cationic
- electrodeposition coating
- epoxy resin
- coating composition
- parts
- Prior art date
Links
Classifications
-
- 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
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4028—Isocyanates; Thioisocyanates
-
- 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
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
-
- 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
- C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
- C09D5/443—Polyepoxides
-
- 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
- C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
- C09D5/443—Polyepoxides
- C09D5/4457—Polyepoxides containing special additives, e.g. pigments, polymeric particles
-
- 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
- C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
- C09D5/4465—Polyurethanes
-
- 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
- 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
- C25D13/22—Servicing or operating apparatus or multistep processes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/02—Electrolytic coating other than with metals with organic materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
Definitions
- the present invention relates to a composition for cationic electrodeposition coating and a method for forming an electrodeposition coating film using the same, and in particular, a cationic electrodeposition coating composition excellent in coating film depositability in a clearance portion of an object to be coated and the use thereof.
- the present invention relates to a method for forming an electrodeposition coating film.
- Cationic electrodeposition coating can be applied to the details even if the object has a complicated shape, and can be applied automatically and continuously. It has been widely put into practical use as an undercoating method for objects having a shape.
- Cationic electrodeposition coating is performed by immersing an object to be coated in a cationic electrodeposition paint as a cathode and applying a voltage.
- the deposition of the coating film in the process of cationic electrodeposition is due to an electrochemical reaction, and the coating film is deposited on the surface of the object to be coated by applying a voltage. Since the deposited coating has insulating properties, the electrical resistance of the coating increases as the deposition of the coating proceeds and the thickness of the deposited film increases in the coating process. As a result, the amount of paint deposited at the site where the coating has already been deposited decreases, and instead, deposition of the coating on the undeposited site begins. In this way, paint solids are sequentially deposited on the object to be coated to complete the coating. In this specification, the property that a coating film is sequentially formed on an unattached portion of an object to be coated is called throwing power.
- Patent Document 1 describes an electrodeposition coating film forming method that can improve throwing power without causing a decrease in coating film appearance due to gas pinholes or the like.
- the coating film is more difficult to be deposited as it is located farther from the opening of the gap.
- the gap structure is sealed and the bag portion is in the shape of a cylinder or a rectangular parallelepiped
- the deposition of the coating film becomes more difficult as it is located in the gap, particularly in the back from the opening.
- the object to be coated is a structure formed by connecting a plurality of steel plates, and the connecting portion of the plurality of steel plates has a gap between the steel plates stacked for connection. In this case, it is difficult to form a coating film inside the gap, and the coating tends to be incomplete.
- the inside of the narrow gap formed in the article to be coated is generally referred to as a “clearance portion”.
- the gap between the steel sheets is 300 ⁇ m or less, the depositability of the electrodeposition coating film on the inside of the gap is clearly lowered.
- the gap is 100 ⁇ m or less, the deposition property of the electrodeposition coating film is further lowered, and when the distance from the opening of the gap is 5 mm or more, a portion where no coating film is formed remains in the back of the gap. End up.
- the present invention solves the above-mentioned conventional problems, and its object is to provide a cationic electrodeposition coating composition exhibiting excellent coating depositability even in the clearance portion of an object to be coated, and electrodeposition using the same. It is providing the coating-film formation method.
- the present invention is a cationic electrodeposition coating composition
- the cationic electrodeposition coating composition contains a cationic epoxy resin (A), a block polyisocyanate curing agent (B), a hydrophobic agent (C), a viscosity modifier (D) and a neutralizing acid in an aqueous medium.
- the solid content mass ratio (A) / (B) between the cationic epoxy resin (A) and the block polyisocyanate curing agent (B) is 60/40 to 80/20
- the hydrophobic agent (C) is a compound having an SP value of 0.6 to 1.0 lower than that of the cationic epoxy resin (A), and the content thereof is the same as that of the cationic epoxy resin (A) and the block.
- the viscosity modifier (D) is resin particles, and the content thereof is the total amount of the cationic epoxy resin (A), the block polyisocyanate curing agent (B), and the hydrophobic agent (C). 3 to 10% by mass with respect to The Coulomb efficiency of the cationic electrodeposition coating composition is 2.0 to 2.5 mg / ( ⁇ m ⁇ C),
- the hydrophobic agent (C) is a non-crosslinked acrylic resin; A cationic electrodeposition coating composition is provided.
- the viscosity modifier (D) is a crosslinked resin particle having an average particle diameter of 50 to 200 nm.
- the present invention is an electrodeposition coating film forming method for immersing an object to be coated in a cationic electrodeposition coating composition, applying a voltage to deposit a coating film, and then performing a process of baking and curing,
- the cationic electrodeposition coating composition contains a cationic epoxy resin (A), a block polyisocyanate curing agent (B), a hydrophobic agent (C), a viscosity modifier (D) and a neutralizing acid in an aqueous medium.
- the solid content mass ratio (A) / (B) between the cationic epoxy resin (A) and the block polyisocyanate curing agent (B) is 60/40 to 80/20
- the hydrophobic agent (C) is a compound having an SP value of 0.6 to 1.0 lower than that of the cationic epoxy resin (A), and the content thereof is the same as that of the cationic epoxy resin (A) and the block. 0.2 to 5.0% by mass with respect to the total amount with the polyisocyanate curing agent (B)
- the viscosity modifier (D) is resin particles, and the content thereof is a total amount of the cationic epoxy resin (A), the block polyisocyanate curing agent (B), and the hydrophobic agent (C).
- the Coulomb efficiency of the cationic electrodeposition coating composition is 2.0 to 2.5 mg / ( ⁇ m ⁇ C)
- the hydrophobic agent (C) is a non-crosslinked acrylic resin
- the voltage boosting speed is 30 to 70 V / 10 sec.
- the object to be coated is a structure formed by connecting a plurality of steel plates, and the connecting portions of the plurality of steel plates have a gap between the steel plates stacked for connection. It is what you have.
- interval of the narrowest part of the said clearance gap is 300 micrometers or less.
- the cationic epoxy resin (A) has an SP value of 11.2 to 11.6, and the hydrophobic agent (C) has an SP value of 10.2 to 10.6.
- the viscosity modifier (D) is a crosslinked resin particle having an average particle diameter of 50 to 200 nm.
- the cationic electrodeposition coating composition of the present invention and the electrodeposition coating film forming method using the same are excellent in coating depositability in the clearance part, that is, excellent in gap coating properties, and even when the object to be coated has a narrow gap. Excellent rust resistance can be imparted.
- the cationic electrodeposition coating composition of the present invention comprises an aqueous medium, a binder resin emulsion dispersed or dissolved in the aqueous medium, a hydrophobic agent (C), a viscosity modifier (D), Contains neutralizing acid, organic solvent and the like.
- the cationic electrodeposition coating composition of the present invention may further contain a pigment.
- the binder resin contained in the binder resin emulsion is a resin component composed of a cationic epoxy resin (A) and a blocked isocyanate curing agent (B).
- A cationic epoxy resin
- B blocked isocyanate curing agent
- the cationic epoxy resin (A) includes an epoxy resin modified with an amine.
- This cationic epoxy resin may be a known resin described in JP-B Nos. 54-4978 and 56-34186.
- Cationic epoxy resins typically open all of the epoxy rings of a bisphenol-type epoxy resin with an active hydrogen compound capable of introducing a cationic group, or some epoxy rings with other active hydrogen compounds. It is produced by opening the ring and opening the remaining epoxy ring with an active hydrogen compound capable of introducing a cationic group.
- 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
- Epicoat 1001 (Same, Epoxy Equivalent 450-500)
- Epicoat 1010 (Same, Epoxy Equivalent 3,000-4,000)
- Epicoat 807 (epoxy equivalent 170).
- R is a residue obtained by removing a glycidyloxy group from a diglycidyl compound
- R ′ is a residue obtained by removing an isocyanate group from polyurethane diisocyanate
- n is an integer of 1 to 5.
- An oxazolidone ring-containing epoxy resin represented by the formula (1) may be used for the cationic epoxy resin. This is because a coating film having excellent heat resistance and corrosion resistance can be obtained.
- an oxazolidone ring into an epoxy resin for example, 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, and a by-product lower alcohol is introduced from the system. Obtained by distilling off.
- an epoxy resin containing an oxazolidone ring can be obtained by reacting a bifunctional epoxy resin with a diisocyanate blocked with a monoalcohol (ie, bisurethane).
- a monoalcohol ie, bisurethane
- Specific examples and production methods of this oxazolidone ring-containing epoxy resin are described, for example, in paragraphs 0012 to 0047 of JP-A No. 2000-128959.
- epoxy resins may be modified with an appropriate resin such as polyester polyol, polyether polyol, and monofunctional alkylphenol.
- the epoxy resin can be extended in chain length by utilizing a reaction between an epoxy group and a diol or dicarboxylic acid.
- epoxy resins are ring-opened with an active hydrogen compound so that an amine equivalent of 0.3 to 4.0 meq / g is obtained after ring opening, and more preferably 5 to 50% of them are occupied by primary amino groups. It is desirable to do.
- active hydrogen compounds capable of introducing a cationic group include primary amines, secondary amines, tertiary amine acid salts, sulfides and acid mixtures.
- a primary, secondary or / and tertiary cationic epoxy resin contained in the cationic electrodeposition coating composition of the present invention a primary amine, secondary amine or tertiary amine acid salt is converted into a cationic group. Is used as an active hydrogen compound that can be introduced.
- ⁇ examples include butylamine, octylamine, diethylamine, dibutylamine, methylbutylamine, monoethanolamine, diethanolamine, N-methylethanolamine, triethylamine hydrochloride, N, N-dimethylethanolamine acetate, diethyl disulfide / acetic acid mixture, etc.
- secondary amines in which primary amines such as aminoethylethanolamine ketimine and diethylenetriamine diketimine are blocked. A plurality of amines may be used in combination.
- the cationic epoxy resin has a solubility parameter (SP value) of 11.2 to 11.6, preferably 11.4 to 11.6. If the SP value of the cationic epoxy resin is less than 11.2, the adhesion between the electrodeposition coating film and the object to be coated may be insufficient, and the rust prevention property may be lowered. May decrease.
- SP value solubility parameter
- the SP value is an index that objectively expresses the ease of dissolution of different types of substances.
- the SP value indicates that the larger the value, the higher the polarity, and the smaller the value, the lower the polarity.
- the SP value of a substance is specified by actual measurement or calculation.
- a method for specifying the SP value is known, and can be measured by, for example, the following method [References: SUH, CLARKE, J. et al. P. S. A-1, 5, 1671-1681 (1967)]. Measurement temperature: 20 ° C Sample: Weigh 0.5 g of resin in a 100 ml beaker, add 10 ml of good solvent using a whole pipette, and dissolve with a magnetic stirrer. solvent: Good solvent ...
- tetrahydrofuran poor solvent ... n-hexane, ion-exchanged water, etc.
- Muddy point measurement The poor solvent is dropped using a 50 ml burette, and the point at which turbidity is caused is defined as the dropping amount.
- the SP value ⁇ of the resin is given by the following equation.
- the SP value can be adjusted by increasing or decreasing the amount of components used during synthesis.
- Specific methods for adjusting the SP value are well known.
- Block isocyanate curing agent (B) The blocked isocyanate curing agent (B) contained in the cationic electrodeposition coating composition of the present invention is a compound obtained by blocking the isocyanate group of polyisocyanate.
- Polyisocyanate refers to a compound having two or more isocyanate groups in one molecule.
- the polyisocyanate may be, for example, any of aliphatic, alicyclic, aromatic and aromatic-aliphatic.
- polyisocyanates include aromatic diisocyanates such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), p-phenylene diisocyanate, and naphthalene diisocyanate; hexamethylene diisocyanate (HDI), 2,2,4- C3-C12 aliphatic diisocyanates such as trimethylhexane diisocyanate and lysine diisocyanate; 1,4-cyclohexane diisocyanate (CDI), isophorone diisocyanate (IPDI), 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI) , Methylcyclohexane diisocyanate, isopropylidene dicyclohexyl-4,4'-diisocyanate, and 1,3-diisocyanatomethyl Carbon such as hexane (hydrogenated XD
- Aliphatic diisocyanates having a number of 5 to 18 aliphatic diisocyanates having an aromatic ring such as xylylene diisocyanate (XDI) and tetramethylxylylene diisocyanate (TMXDI); modified products of these diisocyanates (urethanes, carbodiimides, Uretdione, uretoimine, burette and / or isocyanurate modified product); and the like. These may be used alone or in combination of two or more.
- XDI xylylene diisocyanate
- TXDI tetramethylxylylene diisocyanate
- modified products of these diisocyanates urethanes, carbodiimides, Uretdione, uretoimine, burette and / or isocyanurate modified product
- Adducts or prepolymers obtained by reacting polyisocyanates with polyhydric alcohols such as ethylene glycol, propylene glycol, trimethylolpropane and hexanetriol at an NCO / OH ratio of 2 or more may also be used as the block isocyanate curing agent.
- the blocking agent is added to the polyisocyanate group and is stable at room temperature, but is released when heated above the dissociation temperature and can regenerate the isocyanate group.
- the blocking agent those usually used such as ⁇ -caprolactam and butyl cellosolve can be used. However, among these, many volatile blocking agents are regulated as targets of HAPs, and it is preferable that the amount used is minimized.
- the hydrophobic agent (C) is a water-insoluble compound and is a component that facilitates movement of bubbles that are generated simultaneously with the deposition of the coating film in the process of electrodeposition coating. If air bubbles easily move from the surface of the deposited coating, if the object to be coated has a narrow gap as a structure, the bubbles are easily removed from the inside of the narrow gap, and as a result, the coating is deposited inside the gap. It becomes easy.
- Non-crosslinked acrylic resin is used as the hydrophobic agent.
- Non-crosslinked acrylic resin refers to an acrylic resin prepared without the use of crosslinkable monomers that provide internal crosslinking.
- the non-crosslinked acrylic resin can be prepared by arbitrarily selecting, for example, a hydroxyl group-containing ethylenically unsaturated monomer, an acidic group-containing ethylenically unsaturated monomer, and other ethylenically unsaturated monomers and copolymerizing them.
- Methods for preparing non-crosslinked acrylic resins are known and are described, for example, in paragraphs 0056 to 0059 of JP-A-2009-235350.
- a preferred non-crosslinkable acrylic resin is 20 to 30% by mass of styrene, 15 to 50% by mass of isobutyl methacrylate, 5 to 40% by mass of ethylhexyl acrylate, and 0 to 40% by mass of ethyl acrylate, with the total amount of monomers being 100% by mass. And polymerized from 5 to 20% by mass of hydroxyethyl methacrylate.
- Such a non-crosslinked acrylic resin has a glass transition temperature of 20 to 40 ° C., a number average molecular weight of 2,500 to 3,500, and a hydroxyl value of 30 to 50 mgKOH / g. The number average molecular weight can be measured from the measurement result of gel permeation chromatography (GPC) using polystyrene as a standard.
- the non-crosslinked acrylic resin has an SP value of 10.2 to 10.6, preferably 10.2 to 10.4. If the SP value of the non-crosslinked acrylic resin is less than 10.2, the adhesion between the electrodeposition coating film and the article to be coated may be insufficient, and the rust prevention property may be lowered. May decrease.
- the non-crosslinked acrylic resin has an SP value of 0.6 to 1.0, preferably 0.8 to 1.0, more preferably 0.9 to 1.0, relative to the SP value of the cationic epoxy resin (A).
- a low value is preferred. If the SP value of the non-crosslinked acrylic resin is less than 1.0 lower than the SP value of the resin (A), the compatibility may be insufficient and the finish of the coating may be reduced. On the other hand, if the value exceeds 0.6, there is a possibility that the gap paintability is lowered.
- Viscosity modifier is an insoluble fine particle and is a component that increases the viscosity of the electrodeposition coating composition.
- the viscosity of the electrodeposition coating composition is increased, when the article to be coated has a narrow gap as a structure, the end of the article to be coated constituting the narrow gap is easily covered.
- Resin particles are used as the viscosity modifier.
- Preferred resin particles are acrylic resin particles having an internal cross-linked structure.
- Acrylic resin particles having an internally crosslinked structure can be obtained by emulsion polymerization of a polyfunctional polymerizable unsaturated compound (a) and another polymerizable monomer (b) in the presence of an emulsifier and an initiator.
- the resin particles are crosslinked resin particles having an average particle diameter of 50 to 200 nm, preferably 80 to 170 nm, more preferably 100 to 130 nm. If the average particle diameter of the resin particles is less than 50 nm, the gap paintability may be lowered, and if it exceeds 200 nm, the paint finish may be lowered.
- the average particle diameter of the resin particles contained in the cationic electrodeposition coating composition of the present invention is a volume average particle diameter and can be measured by a granular particle permeation measurement method. Examples of equipment that can be used for measuring the average particle diameter of the resin particles include MICROTRAC 9340UPA manufactured by Nikkiso Co., Ltd.
- the average particle size is measured by measuring the particle size distribution of the resin particles using the refractive index of the solvent (water) 1.33 and the refractive index of the resin (depending on the type of resin. For example, 1.59 for acrylic resins).
- Electrodeposition paints contain pigments as colorants.
- the cationic electrodeposition coating composition of the present invention may contain a pigment that is usually used as necessary.
- pigments include colored pigments such as titanium white, carbon black and bengara, extender pigments such as kaolin, talc, aluminum silicate, calcium carbonate, mica, clay and silica, zinc phosphate, iron phosphate, Rust preventive pigments such as aluminum phosphate, calcium phosphate, zinc phosphite, zinc cyanide, zinc oxide, aluminum tripolyphosphate, zinc molybdate, aluminum molybdate, calcium molybdate and aluminum phosphomolybdate, aluminum phosphomolybdate Etc.
- Pigment-dispersed paste When a pigment is used as a component of an electrodeposition paint, generally the pigment is dispersed in advance in an aqueous medium at a high concentration to form a paste. This is because the pigment is in a powder form, and it is difficult to disperse it in a single step in a low concentration uniform state used in the electrodeposition paint. Such a paste is generally called a pigment dispersion paste.
- the pigment dispersion paste is prepared by dispersing a pigment in an aqueous medium together with a pigment dispersion resin.
- a pigment dispersion resin 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 sulfonium group is generally used.
- aqueous medium ion-exchanged water or water containing a small amount of alcohol is used.
- the pigment dispersion resin is used in a solid content ratio of 5 to 40 parts by mass, and the pigment is used in a solid content ratio of 20 to 50 parts by mass.
- the cationic electrodeposition coating composition comprises a cationic epoxy resin (A), a blocked isocyanate curing agent (B), a hydrophobic agent (C), a viscosity modifier (D), a pigment dispersion paste, It is prepared by dispersing or dissolving components such as neutralizing acid and organic solvent in an aqueous medium.
- the content of the blocked isocyanate curing agent (B) is the active hydrogen-containing functional group such as a primary, secondary or / and tertiary amino group or hydroxyl group in the cationic epoxy resin at the time of curing. It must be sufficient to react to give a good cured coating, generally expressed in terms of the solids mass ratio of the cationic epoxy resin (A) to the blocked isocyanate curing agent (B), generally 60 / 40-80 / 20, preferably in the range of 65/35 to 75/25.
- the content (solid content) of the hydrophobic agent (C) is based on the total amount (solid content) of the cationic epoxy resin (A) and the blocked polyisocyanate curing agent (B) in the cationic electrodeposition coating composition. It is 0.2 to 5% by mass, preferably 1.5 to 5% by mass, and more preferably 3 to 5% by mass. If the content of the hydrophobic agent is less than 0.2% by mass, the gap coating property may be lowered, and if it exceeds 5% by mass, the rust prevention property may be lowered.
- the content (solid content) of the viscosity modifier (D) is the total amount of the cationic epoxy resin (A), the blocked polyisocyanate curing agent (B) and the hydrophobic agent (C) in the cationic electrodeposition coating composition. It is 3 to 10% by mass, preferably 5 to 9% by mass, and more preferably 6 to 8% by mass with respect to (solid content). If the content of the viscosity modifier is less than 3% by mass, the gap coatability may decrease, and if it exceeds 10% by mass, the finish of coating may decrease.
- the cationic electrodeposition coating composition contains a neutralizing acid in order to neutralize the cationic epoxy resin and improve the dispersibility of the binder resin emulsion.
- the neutralizing acid is an inorganic or organic acid such as hydrochloric acid, nitric acid, phosphoric acid, formic acid, acetic acid, lactic acid.
- the amount of the neutralizing acid contained in the coating composition is increased, the neutralization rate of the cationic epoxy resin is increased, the affinity of the binder resin particles to the aqueous medium is increased, and the dispersion stability is increased. This means that the binder resin hardly deposits on the object to be coated during electrodeposition coating, and the depositability of the solid content of the paint is lowered.
- the amount of the neutralizing acid contained in the coating composition is small, the neutralization rate of the cationic epoxy resin is lowered, the affinity of the binder resin particles to the aqueous medium is lowered, and the dispersion stability is reduced. This means that the binder resin tends to precipitate on the object to be coated at the time of coating, and the precipitation of paint solids increases.
- the content of the neutralizing acid in the cationic electrodeposition coating composition is such that the Coulomb efficiency of the cationic electrodeposition coating composition is 2.0 to 2.5 mg / ( ⁇ m ⁇ C), preferably 2.2 to 2.5 mg / ( ⁇ m ⁇ C), more preferably 2.4 to 2.5 mg / ( ⁇ m ⁇ C). If the coulomb efficiency of the cationic electrodeposition coating composition is less than 2.0 mg / ( ⁇ m ⁇ C), there is a possibility that the gap coatability may be reduced. If it exceeds 2.5 mg / ( ⁇ m ⁇ C), the entrance of the gap Precipitation of the liquid is preceded so that the gap is closed and positioned further away from the opening of the gap, the precipitation becomes insufficient and the gap paintability may be reduced.
- ⁇ ⁇ Coulomb efficiency is an index that represents the precipitation of paint solids. That is, the unit charge amount (coulomb) consumed by passing an electric current and the amount (mg) of the deposited paint per unit thickness of the deposited coating film.
- the coulomb efficiency is measured by electrodeposition coating a sample for measurement prepared by adding a certain amount of a curing agent and water to a cationic epoxy resin to be measured at a constant voltage (180 to 280 V), and obtaining the obtained electrodeposition. It can identify from the quantity of the obtained cured electrodeposition coating film by measuring the mass of the cured electrodeposition coating film which baked and hardened the coating film.
- the neutralizing acid is used in such an amount that the milligram equivalent (meq) of the acid per 100 g of resin solid content of the cationic electrodeposition coating composition is in the range of 15-25.
- the cationic electrodeposition coating composition can contain a tin compound such as dibutyltin dilaurate and dibutyltin oxide and a usual urethane cleavage catalyst. Since those substantially free of lead are preferable, the amount of the tin compound and the urethane cleavage catalyst is preferably 0.1 to 5% by mass of the block polyisocyanate compound.
- the cationic electrodeposition coating composition may contain conventional paint additives such as water-miscible organic solvents, surfactants, antioxidants, ultraviolet absorbers, and pigments.
- Electrodeposition coating formation method The above-mentioned cationic electrodeposition coating composition is electrodeposited on an object to be coated, and an electrodeposition film is formed on the surface of the object to be coated.
- the material to be coated is not particularly limited as long as it is electrically conductive, and examples thereof include iron plates, steel plates, aluminum plates, those obtained by surface treatment thereof, and molded products thereof.
- the object to be coated has a narrow gap as a structure.
- the object to be coated is a structure formed by connecting a plurality of steel plates, and the connecting portion of the plurality of steel plates has a gap between the steel plates stacked for connection. It is.
- the minimum value of the gap between the steel plates may be 300 ⁇ m or less, and the minimum value of the gap may be 100 ⁇ m or less.
- Specific examples of such objects include automobile bodies and outdoor electrical equipment.
- Electrodeposition is generally a process of immersing a coating in a cationic electrodeposition coating composition, and a process of depositing a coating film by applying a voltage between the coating as a cathode and an anode. Composed. When applying the voltage, it is preferable to gradually increase the voltage.
- the pressure increasing speed in the process of electrodeposition coating is 30 to 70 V / 10 seconds, preferably 45 to 70 V / 10 seconds, more preferably 60 to 70 V / 10 seconds. If the pressure increase rate is less than 30 V / 10 seconds, the gap coatability may be lowered, and if it exceeds 70 V / 10 seconds, the gap coatability may also be lowered.
- the boosting rate is preferably constant until a predetermined voltage condition is reached.
- the voltage application time varies depending on the electrodeposition conditions, but can generally be 2 to 4 minutes.
- a cured electrodeposition coating film is obtained by baking at 120 to 260 ° C., preferably 140 to 220 ° C. for 10 to 30 minutes.
- Production Example 2 Production of amine-modified epoxy resin (A) 71.34 parts of 2,4 / 2,6-tolylene diisocyanate (80/20 wt%) and methyl were added to a flask equipped with a stirrer, a cooler, a nitrogen injection tube and a dropping funnel. 111.98 parts of isobutyl ketone and 0.02 part of dibutyltin dilaurate were weighed, and 14.24 parts of methanol was added dropwise from a dropping funnel over 30 minutes while stirring and nitrogen bubbling. The temperature was raised from room temperature to 60 ° C. due to heat generation.
- Production Example 4 Production of Pigment Dispersion Paste 211 parts of pigment dispersion resin obtained in Production Example 3, 192.0 parts of titanium dioxide, 8.0 parts of dibutyltin oxide and 78 parts of ion-exchanged water were added to a sand grind mill until the particle size became 10 ⁇ m or less. Dispersion gave a pigment dispersion paste (solid content 56%).
- the SP value of the obtained non-crosslinked acrylic resin (1) was 10.5, the glass transition temperature was 20 ° C., and the number average molecular weight was 5,600.
- the obtained non-crosslinked acrylic resin (2) had an SP value of 10.9, a glass transition temperature of 40 ° C., and a number average molecular weight of 5,800.
- the resulting dispersion of the crosslinked resin particles A had a non-volatile content of 36%, a pH of 5.0, and an average particle size of 110 nm.
- Production Example 8 Production of cross-linked resin particles B The same procedure as in Production Example 7 except that the amount of deionized water used in the resin solution 1 was changed from 270 parts to 200 parts, and the amount of deionized water used in the pre-emulsion was changed from 250 parts to 320 parts. A dispersion of resin particles B was obtained. The resulting dispersion of the crosslinked resin particles B had a nonvolatile content of 35%, a pH of 5.0, and an average particle size of 250 nm.
- Production Example 9 Production of cationic electrodeposition coating composition 1 used in Examples 1, 4 and 6 Production of 150 parts of amine-modified epoxy resin of Production Example 2 in which 100 parts of ion-exchanged water and 7 parts of acetic acid were weighed and heated to 70 ° C. A mixture of 10 parts of the hydrophobic agent (non-crosslinked acrylic resin) (1) of Example 5 and 100 parts of the blocked isocyanate curing agent of Production Example 1 was gradually added dropwise and stirred to uniformly disperse. Thereafter, ion exchange water was added to adjust the solid content to 38%.
- a cationic electrodeposition coating composition 1 having 6% by mass of crosslinked resin particles A, 3% by mass of non-crosslinked acrylic resin, and 20% by mass of solid content was obtained.
- Cationic electrodeposition coating composition 1 was used for electrodeposition coating so as to form a coating film having a thickness of 15 ⁇ m at a bath temperature of 30 ° C.
- the coating voltage in this coating and the residual current at the end of electrodeposition were measured, and the coating film resistance value (k ⁇ ⁇ cm 2 ) was calculated from these values.
- the formula is
- Production Example 10 Production of cationic electrodeposition coating composition 2 used in Examples 2, 8 and 9
- the amount of amine-modified epoxy resin in Production Example 2 was changed to 175 parts, and the amount of blocked isocyanate curing agent in Production Example 1 was changed to 75 parts. Except for the above, a cationic electrodeposition coating composition 2 was obtained in the same manner as in Production Example 9, and the characteristics were measured.
- Production Example 11 Production of cationic electrodeposition coating composition 3 used in Examples 3, 5 and 7
- the amount of amine-modified epoxy resin of Production Example 2 was changed to 200 parts, and the amount of blocked isocyanate curing agent of Production Example 1 was changed to 50 parts. Except for the above, a cationic electrodeposition coating composition 3 was obtained in the same manner as in Production Example 9, and the characteristics were measured.
- Production Example 12 Production of cationic electrodeposition coating composition 4 used in Comparative Example 1 Hydrophobic agent (non-crosslinked acrylic resin) of Production Example 5 instead of 10 parts of hydrophobic agent (non-crosslinked acrylic resin) of Production Example 5 (1) (2) A cationic electrodeposition coating composition 4 was obtained in the same manner as in Production Example 10 except that 10 parts were used, and the characteristics were measured.
- Production Example 13 Production of cationic electrodeposition coating composition 5 used in Comparative Example 2 Production except that the amount of amine-modified epoxy resin in Production Example 2 was changed to 90 parts and the amount of blocked isocyanate curing agent in Production Example 1 was changed to 10 parts. Cationic electrodeposition coating composition 5 was obtained in the same manner as in Example 9, and the characteristics were measured.
- Production Example 14 Production of cationic electrodeposition coating composition 6 used in Comparative Example 3 Production except that the amount of amine-modified epoxy resin in Production Example 2 was changed to 55 parts and the amount of blocked isocyanate curing agent in Production Example 1 was changed to 45 parts. In the same manner as in Example 9, a cationic electrodeposition coating composition 6 was obtained, and the characteristics were measured.
- Production Example 15 Production of cationic electrodeposition coating composition 7 used in Comparative Example 4 175 parts of amine-modified epoxy resin of Production Example 2 obtained by weighing 100 parts of ion-exchanged water and 7 parts of acetic acid and heating to 70 ° C., hydrophobic of Production Example 5 A mixture of 10 parts of an agent (non-crosslinked acrylic resin) (1) and 75 parts of the blocked isocyanate curing agent of Production Example 1 was gradually added dropwise and stirred to uniformly disperse. Thereafter, ion exchange water was added to adjust the solid content to 38%.
- Production Example 16 Production of Cationic Electrodeposition Coating Composition 8 Used in Example 10 Production Example except that 10 parts of the hydrophobic agent (non-crosslinked acrylic resin) (1) of Production Example 5 was changed to 0.7 parts. In the same manner as in Example 9, a cationic electrodeposition coating composition 8 was obtained, and the characteristics were measured.
- Production Example 17 Production of cationic electrodeposition coating composition 9 used in Comparative Example 5 Cationic electrodeposition coating composition in the same manner as in Production Example 9 except that 8 parts of the crosslinked resin particles A in Production Example 7 were changed to 20 parts. 9 was obtained and the characteristics were measured.
- Production Example 18 Production of cationic electrodeposition coating composition 10 used in Example 11 In the same manner as in Production Example 9, except that 8 parts of crosslinked resin particles B of Production Example 8 were used instead of 8 parts of crosslinked resin particles A of Production Example 7. Thus, a cationic electrodeposition coating composition 10 was obtained, and the characteristics were measured.
- Example 1 Cationic electrodeposition coating composition 1
- Two cold-rolled steel plates treated with zinc phosphate of 0.8 mm ⁇ 70 mm ⁇ 150 mm were prepared as coating objects, and two stainless steel plates of 12.7 mm ⁇ 50 mm ⁇ 100 ⁇ m were prepared as spacers.
- Two sheets of the object to be coated were stacked, and a spacer was sandwiched and fixed so that the sides of the spacer coincided with the two sides of the corner of the object to be coated. As a result, a gap having a width of 44.6 mm and an interval of 100 ⁇ m was formed at the center of one side of the two objects to be coated.
- 4,000 ml of the cationic electrodeposition coating composition 1 prepared in Production Example 9 was placed in an electrodeposition tank, and the object to be coated was immersed to a depth of 85 mm with one side where a gap was formed facing downward.
- the electrodeposition tank and the object to be coated were connected to a power source, the voltage was increased to a coating voltage of 180 V under a pressure increase condition of 50 V / 10 seconds, and energized for 180 seconds to deposit a coating film on the surface of the object to be coated.
- the steel sheet with the coating film attached was taken out from the electrodeposition bath, washed with water, and baked at 170 ° C. for 20 minutes to obtain an electrodeposited steel sheet.
- the arithmetic average roughness (Ra) of the outer painted surface of the electrodeposited steel sheet was measured using an evaluation type surface roughness measuring machine (SURFTEST SJ-201P, manufactured by Mitutoyo Corporation). At that time, measurement was performed 7 times using a sample with a 2.5 mm width cut-off (number of sections: 5), and the measured value was determined by averaging up and down.
- the evaluation criteria were as follows.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Molecular Biology (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Description
前記カチオン電着塗料組成物は、水性媒体中にカチオン性エポキシ樹脂(A)、ブロックポリイソシアネート硬化剤(B)、疎水性剤(C)、粘度調整剤(D)及び中和酸を含有し、
前記カチオン性エポキシ樹脂(A)と前記ブロックポリイソシアネート硬化剤(B)との固形分質量比(A)/(B)が60/40~80/20であり、
前記疎水性剤(C)は、SP値がカチオン性エポキシ樹脂(A)に対し0.6~1.0低い化合物であって、その含有量が、前記カチオン性エポキシ樹脂(A)と前記ブロックポリイソシアネート硬化剤(B)との合計量に対して0.2~5質量%であり、
前記粘度調整剤(D)は、樹脂粒子であって、その含有量が、前記カチオン性エポキシ樹脂(A)と前記ブロックポリイソシアネート硬化剤(B)と前記疎水性剤(C)との合計量に対して3~10質量%であり、
前記カチオン電着塗料組成物のクーロン効率が、2.0~2.5mg/(μm・C)であり、
前記疎水性剤(C)が非架橋アクリル樹脂である、
カチオン電着塗料組成物を提供する。
前記カチオン電着塗料組成物は、水性媒体中にカチオン性エポキシ樹脂(A)、ブロックポリイソシアネート硬化剤(B)、疎水性剤(C)、粘度調整剤(D)及び中和酸を含有し、
前記カチオン性エポキシ樹脂(A)と前記ブロックポリイソシアネート硬化剤(B)との固形分質量比(A)/(B)が60/40~80/20であり、
前記疎水性剤(C)は、SP値がカチオン性エポキシ樹脂(A)に対し0.6~1.0低い化合物であって、その含有量が、前記カチオン性エポキシ樹脂(A)と前記ブロックポリイソシアネート硬化剤(B)との合計量に対して0.2~5.0質量%であり、
前記粘度調整剤(D)が、樹脂粒子であって、その含有量が、前記カチオン性エポキシ樹脂(A)と前記ブロックポリイソシアネート硬化剤(B)と前記疎水性剤(C)との合計量に対して3.0~10.0質量%であり、
前記カチオン電着塗料組成物のクーロン効率が、2.0~2.5mg/(μm・C)であり、
前記疎水性剤(C)が非架橋アクリル樹脂であり、
前記電圧の昇圧速度が30~70V/10secである、
電着塗膜形成方法を提供する。
本発明のカチオン電着塗料組成物は、水性媒体、水性媒体中に分散するか又は溶解したバインダー樹脂エマルション、疎水性剤(C)、粘度調整剤(D)、中和酸、有機溶媒等を含有する。本発明のカチオン電着塗料組成物はさらに顔料を含んでもよい。バインダー樹脂エマルションに含有されるバインダー樹脂は、カチオン性エポキシ樹脂(A)およびブロックイソシアネート硬化剤(B)からなる樹脂成分である。以下、それぞれの成分について説明する。
カチオン性エポキシ樹脂(A)には、アミンで変性されたエポキシ樹脂が含まれる。このカチオン性エポキシ樹脂は、特公昭54-4978号、特公昭56-34186号などに記載されている公知の樹脂であってよい。
で示されるオキサゾリドン環含有エポキシ樹脂をカチオン性エポキシ樹脂に用いてもよい。耐熱性及び耐食性に優れた塗膜が得られるからである。
測定温度:20℃
サンプル:樹脂0.5gを100mlビーカーに秤量し、良溶媒10mlをホールピペットを用いて加え、マグネティックスターラーにより溶解する。
溶媒:
良溶媒…テトラヒドロフラン
貧溶媒…n-ヘキサン、イオン交換水など
濁点測定:50mlビュレットを用いて貧溶媒を滴下し、濁りが生じた点を滴下量とする。
φi:濁点における各溶媒の体積分率
δi:溶媒のSP値
ml:低SP貧溶媒混合系
mh:高SP貧溶媒混合系
本発明のカチオン電着塗料組成物に含まれるブロックイソシアネート硬化剤(B)は、ポリイソシアネートのイソシアネート基をブロック化した化合物である。ポリイソシアネートとは、1分子中にイソシアネート基を2個以上有する化合物をいう。ポリイソシアネートとしては、例えば、脂肪族系、脂環式系、芳香族系および芳香族-脂肪族系等のうちのいずれのものであってもよい。
疎水性剤(C)は非水溶性の化合物であり、電着塗装の過程で塗膜の析出と同時に発生してしまう気泡を移動し易くする成分である。析出した塗膜の表面から気泡が移動し易いと、被塗物が構造として狭い隙間を有する場合、狭い隙間の内部から気泡が除去され易くなり、結果として、隙間の内部に塗膜が析出し易くなる。
粘度調整剤は非溶解性の微粒子であり、電着塗料組成物の粘度を上昇させる成分である。電着塗料組成物の粘度が上昇すると、被塗物が構造として狭い隙間を有する場合、狭い隙間を構成する被塗物の端部が被覆され易くなる。
一般に、電着塗料には着色剤として顔料を含有させる。本発明のカチオン電着塗料組成物にも必要に応じて通常用いられる顔料を含有させる。かかる顔料の例としては、チタンホワイト、カーボンブラック及びベンガラのような着色顔料、カオリン、タルク、ケイ酸アルミニウム、炭酸カルシウム、マイカ、クレー及びシリカのような体質顔料、リン酸亜鉛、リン酸鉄、リン酸アルミニウム、リン酸カルシウム、亜リン酸亜鉛、シアン化亜鉛、酸化亜鉛、トリポリリン酸アルミニウム、モリブデン酸亜鉛、モリブデン酸アルミニウム、モリブデン酸カルシウム及びリンモリブデン酸アルミニウム、リンモリブデン酸アルミニウム亜鉛のような防錆顔料等が挙げられる。
顔料を電着塗料の成分として用いる場合、一般に顔料を予め高濃度で水性媒体に分散させてペースト状にする。顔料は粉体状であるため、電着塗料で用いる低濃度均一状態に一工程で分散させるのは困難だからである。一般にこのようなペーストを顔料分散ペーストという。
カチオン電着塗料組成物は、カチオン性エポキシ樹脂(A)、ブロックイソシアネート硬化剤(B)、疎水性剤(C)、粘度調整剤(D)、顔料分散ペースト、中和酸及び有機溶媒等の成分を水性媒体中に分散又は溶解することによって調製される。
上記カチオン電着塗料組成物は被塗物に電着塗装され、被塗物の表面には電着塗膜が形成される。被塗物としては導電性のあるものであれば特に限定されず、例えば、鉄板、鋼板、アルミニウム板及びこれらを表面処理したもの、これらの成型物等を挙げることができる。
ブロックイソシアネート硬化剤(B)の製造
攪拌機、冷却器、窒素注入管、温度計および滴下ロートを取り付けたフラスコにヘキサメチレンジイソシアネートの3量体(日本ポリウレタン社製、コロネートHX)199部とメチルイソブチルケトン32部、およびジブチルスズジラウレート0.03部を量り取り、攪拌、窒素をバブリングしながら、メチルエチルケトオキシム87.0部を滴下ロートより1時間かけて滴下した。温度は50℃からはじめ70℃まで昇温した。そのあと1時間反応を継続し、赤外線分光計によりNCO基の吸収が消失するまで反応させた。その後n-ブタノール0.74部、メチルイソブチルケトン39.93部を加え、不揮発分80%とした。
アミン変性エポキシ樹脂(A)の製造
攪拌機、冷却器、窒素注入管および滴下ロートを取り付けたフラスコに、2,4/2,6-トリレンジイソシアネート(80/20wt%)71.34部と、メチルイソブチルケトン111.98部と、ジブチルスズジラウレート0.02部を量り取り、攪拌、窒素バブリングしながらメタノール14.24部を滴下ロートより30分かけて滴下した。温度は室温から発熱により60℃まで昇温した。その後30分間反応を継続した後、エチレングリコールモノ-2-エチルヘキシルエーテル46.98部を滴下ロートより30分かけて滴下した。発熱により70~75℃へ昇温した。30分間反応を継続した後、ビスフェノールAプロピレンオキシド(5モル)付加体(三洋化成工業社製、BP-5P)41.25部を加え、90℃まで昇温し、IRスペクトルを測定しながらNCO基が消失するまで反応を継続した。
顔料分散樹脂の製造
攪拌機、冷却器、窒素注入管、温度計および滴下ロートを取り付けたフラスコに、エポキシ当量188のビスフェノールA型エポキシ樹脂(ダウケミカル社製、DER-331J)382.20部と、ビスフェノールA111.98部を量り取り、80℃まで昇温し、均一に溶解した後、2-エチル-4-メチルイミダゾール1%溶液1.53部を加え、170℃で2時間反応させた。140℃まで冷却した後、これに2-エチルヘキサノールハーフブロック化イソホロンジイソシアネート(不揮発分90%)196.50部を加え、NCO基が消失するまで反応させた。これにジプロピレングリコールモノブチルエーテル205.00部を加え、続いて1-(2-ヒドロキシエチルチオ)-2-プロパノール408.00部、ジメチロールプロピオン酸134.00部を添加し、イオン交換水144.00部を加え、70℃で反応させた。反応は酸価が5以下になるまで継続した。得られた顔料分散樹脂はイオン交換1150.50部で不揮発分35%に希釈した。
顔料分散ペーストの製造
サンドグラインドミルに製造例3で得た顔料分散樹脂を211部、二酸化チタン192.0部、ジブチルスズオキシド8.0部およびイオン交換水78部を入れ、粒度10μm以下になるまで分散して、顔料分散ペーストを得た(固形分56%)。
疎水性剤(非架橋アクリル樹脂)(1)の製造
還流冷却器、撹拌機、滴下ロートおよび窒素導入管を備えた5つ口フラスコに、酢酸n-ブチル300.0部を仕込み、窒素雰囲気下120℃に加熱保持した。これへ、スチレン200.0部、イソブチルメタクリレート325.6部、2-エチルヘキシルアクリレート150.2部、エチルアクリレート138.6部、ヒドロキシエチルメタクリレート185.6部、酢酸n-ブチル60.0部、およびt-ブチルパーオクトエート180.0部の混合物を滴下ロートから3時間かけて滴下した。滴下終了後120℃に1時間保持した後、酢酸n-ブチル30.0部、およびt-ブチルパーオクトエート10.0部の混合物を滴下し、120℃で30分保持し、固形分70%のアクリル樹脂の溶液を得た。
疎水性剤(非架橋アクリル樹脂)(2)の製造
還流冷却器、撹拌機、滴下ロートおよび窒素導入管を備えた5つ口フラスコに、酢酸n-ブチル300.0部を仕込み、窒素雰囲気下120℃に加熱保持した。これへ、スチレン200.0部、イソブチルメタクリレート478.4部、2-エチルヘキシルアクリレート62.0部、エチルアクリレート74.0部、ヒドロキシエチルメタクリレート185.6部、酢酸n-ブチル60.0部、およびt-ブチルパーオクトエート180.0部の混合物を滴下ロートから3時間かけて滴下した。滴下終了後120℃に1時間保持した後、酢酸n-ブチル30.0部、およびt-ブチルパーオクトエート10.0部の混合物を滴下し、120℃で30分保持し、固形分70%のアクリル樹脂の溶液を得た。
架橋樹脂粒子Aの製造
反応容器に、アンモニウム基を有するアクリル樹脂120部と脱イオン水270部とを加え、75℃で加熱攪拌した。ここに2,2’-アゾビス(2-(2-イミダゾリン-2-イル)プロパン)1.5部の酢酸100%中和水溶液を5分かけて滴下した。5分間エージングした後、メチルメタクリレート30部を5分かけて滴下した(樹脂溶液1)。さらに5分間エージングした後、アンモニウム基を有するアクリル樹脂170部と脱イオン水250部とを混合した溶液にメチルメタクリレート170部、スチレン40部、n-ブチルメタクリレート30部、グリシジルメタクリレート5部およびネオペンチルグリコールジメタクリレート30部からなるエチレン性不飽和モノマー混合物を加え攪拌して得られたプレエマルションを40分かけて滴下した。60分間エージングした後、冷却し、架橋樹脂粒子Aの分散液を得た。得られた架橋樹脂粒子Aの分散液の不揮発分は36%、pHは5.0、平均粒子径は110nmであった。架橋樹脂粒子の平均粒子径は、日機装社製、MICROTRAC9340UPAを用いて、粒状粒子透過測定法にて測定した。また、この測定器において、架橋樹脂粒子の粒度分布を測定し、その測定値から累積相対度数F(x)=0.5における平均粒子径を算出した。これらの測定および算出においては、溶媒(水)の屈折率1.33、樹脂分の屈折率1.59を用いた。
架橋樹脂粒子Bの製造
樹脂溶液1に用いる脱イオン水量を270部から200部に、及びプレエマルションに用いる脱イオン水量を250部から320部に変更した以外は製造例7と同様にして、架橋樹脂粒子Bの分散液を得た。得られた架橋樹脂粒子Bの分散液の不揮発分は35%、pHは5.0、平均粒子径は250nmであった。
実施例1、4、6に使用するカチオン電着塗料組成物1の製造
イオン交換水100部と酢酸7部を量り取り、70℃まで加温した製造例2のアミン変性エポキシ樹脂150部、製造例5の疎水性剤(非架橋アクリル樹脂)(1)10部および製造例1のブロックイソシアネート硬化剤100部の混合物を徐々に滴下し、攪拌して均一に分散させた。そのあとイオン交換水を加え固形分38%に調整した。
カチオン電着塗料組成物1を、一定の電圧(180~280V)で厚さ15μmの塗膜になるように電着塗装し、得られた電着塗膜を焼き付けして硬化させた硬化電着塗膜の質量を測定することによって、得られた硬化電着塗膜の量を測定することにより、クーロン効率を求めた。
カチオン電着塗料組成物1を用いて被塗物に膜厚15μmとなるように電着塗膜を形成し、これを水洗して余分な電着塗料組成物を取り除いた。次いで水分を取り除いた後、乾燥させることなくすぐに塗膜を取り出して、試料を調製した。こうして得られた試料を、回転型動的粘弾性測定装置「Rheosol G-3000」(ユービーエム社製)に装着した。測定条件は、歪み0.5deg、周波数0.02Hz、温度50℃とした。測定開始後、コーンプレート内で電着塗膜が均一に広がった状態となった時点で塗膜の粘度の測定を行った。
カチオン電着塗料組成物1を用いて、浴温30℃において、厚さ15μmの塗膜になるように電着塗装した。この塗装における塗装電圧および電着終了時の残余電流を測定し、これらの値から塗膜抵抗値(kΩ・cm2)を算出した。計算式は、
実施例2、8、9に使用するカチオン電着塗料組成物2の製造
製造例2のアミン変性エポキシ樹脂の量を175部、製造例1のブロックイソシアネート硬化剤の量を75部と変更したこと以外は、製造例9と同様にしてカチオン電着塗料組成物2を得、特性を測定した。
実施例3、5、7に使用するカチオン電着塗料組成物3の製造
製造例2のアミン変性エポキシ樹脂の量を200部、製造例1のブロックイソシアネート硬化剤の量を50部と変更したこと以外は、製造例9と同様にしてカチオン電着塗料組成物3を得、特性を測定した。
比較例1に使用するカチオン電着塗料組成物4の製造
製造例5の疎水性剤(非架橋アクリル樹脂)(1)10部の代わりに、製造例6の疎水性剤(非架橋アクリル樹脂)(2)10部を用いたこと以外は、製造例10と同様にしてカチオン電着塗料組成物4を得、特性を測定した。
比較例2に使用するカチオン電着塗料組成物5の製造
製造例2のアミン変性エポキシ樹脂の量を90部、製造例1のブロックイソシアネート硬化剤の量を10部と変更したこと以外は、製造例9と同様にしてカチオン電着塗料組成物5を得、特性を測定した。
比較例3に使用するカチオン電着塗料組成物6の製造
製造例2のアミン変性エポキシ樹脂の量を55部、製造例1のブロックイソシアネート硬化剤の量を45部と変更したこと以外は、製造例9と同様にしてカチオン電着塗料組成物6を得、特性を測定した。
比較例4に使用するカチオン電着塗料組成物7の製造
イオン交換水100部と酢酸7部を量り取り、70℃まで加温した製造例2のアミン変性エポキシ樹脂175部、製造例5の疎水性剤(非架橋アクリル樹脂)(1)10部および製造例1のブロックイソシアネート硬化剤75部の混合物を徐々に滴下し、攪拌して均一に分散させた。そのあとイオン交換水を加え固形分38%に調整した。
実施例10に使用するカチオン電着塗料組成物8の製造
製造例5の疎水性剤(非架橋アクリル樹脂)(1)10部を0.7部に変更して用いたこと以外は、製造例9と同様にしてカチオン電着塗料組成物8を得、特性を測定した。
比較例5に使用するカチオン電着塗料組成物9の製造
製造例7の架橋樹脂粒子A8部を20部に変更して用いたこと以外は、製造例9と同様にしてカチオン電着塗料組成物9を得、特性を測定した。
実施例11に使用するカチオン電着塗料組成物10の製造
製造例7の架橋樹脂粒子A8部の代わりに、製造例8の架橋樹脂粒子B8部を用いたこと以外は、製造例9と同様にしてカチオン電着塗料組成物10を得、特性を測定した。
カチオン電着塗料組成物1
被塗物として0.8mm×70mm×150mmのリン酸亜鉛処理した冷間圧延鋼板2枚、及びスペーサーとして12.7mm×50mm×100μmのステンレス板2枚を準備した。被塗物を2枚重ね、その間に、被塗物の角部2箇所の辺にスペーサーの辺がそれぞれ一致するようにスペーサーを挟み、固定した。そのことにより、2枚重ねた被塗物の一辺の中央部に、幅44.6mm、間隔100μmの隙間を形成した。
2枚重ねてある電着塗装鋼板を分解し、鋼板内側の隙間部分(2枚のスペーサーの間)に下の辺から塗膜が形成されている高さを測定した。評価基準は次の通りとした。
電着塗装鋼板の外側の塗装面にナイフにて素地に達するクロスカットを入れ、35℃で800時間5%食塩水を塗膜表面に噴霧した。その後、塗膜を水洗し乾燥させた後、ニチバン社製「セロハンテープ」を塗膜表面に指で圧着し、勢いよく剥離した。テープにより、カット部から塗膜が剥離した幅を測定した。評価基準は次の通りとした。
JIS-B0601に準拠し、評価型表面粗さ測定機(ミツトヨ社製、SURFTEST SJ-201P)を用いて、電着塗装鋼板の外側の塗装面の算術平均粗さ(Ra)を測定した。その際、2.5mm幅カットオフ(区画数5)を入れたサンプルを用いて7回測定し、上下消去平均して測定値を決定した。評価基準は次の通りとした。
カチオン電着塗料組成物の種類及び電着塗装の条件を表2及び表3に示すように変更すること以外は実施例1と同様にして、電着塗装鋼板を得、塗膜の析出状態及び性能を評価した。結果を表2及び3に示す。
Claims (7)
- カチオン電着塗料組成物であって、
前記カチオン電着塗料組成物は、水性媒体中にカチオン性エポキシ樹脂(A)、ブロックポリイソシアネート硬化剤(B)、疎水性剤(C)、粘度調整剤(D)及び中和酸を含有し、
前記カチオン性エポキシ樹脂(A)と前記ブロックポリイソシアネート硬化剤(B)との固形分質量比(A)/(B)が60/40~80/20であり、
前記疎水性剤(C)は、SP値がカチオン性エポキシ樹脂(A)に対し0.6~1.0低い化合物であって、その含有量が、前記カチオン性エポキシ樹脂(A)と前記ブロックポリイソシアネート硬化剤(B)との合計量に対して0.2~5質量%であり、
前記粘度調整剤(D)は、樹脂粒子であって、その含有量が、前記カチオン性エポキシ樹脂(A)と前記ブロックポリイソシアネート硬化剤(B)と前記疎水性剤(C)との合計量に対して3~10質量%であり、
前記カチオン電着塗料組成物のクーロン効率が、2.0~2.5mg/(μm・C)であり、
前記疎水性剤(C)が非架橋アクリル樹脂である、
カチオン電着塗料組成物。 - 前記粘度調整剤(D)は、平均粒子径が50~200nmである架橋樹脂粒子である、請求項1記載のカチオン電着塗料組成物。
- カチオン電着塗料組成物中に被塗物を浸漬し、電圧を印加して塗膜を析出させ、その後、焼き付け硬化させる過程を行う電着塗膜形成方法であって、
前記カチオン電着塗料組成物は、水性媒体中にカチオン性エポキシ樹脂(A)、ブロックポリイソシアネート硬化剤(B)、疎水性剤(C)、粘度調整剤(D)及び中和酸を含有し、
前記カチオン性エポキシ樹脂(A)と前記ブロックポリイソシアネート硬化剤(B)との固形分質量比(A)/(B)が60/40~80/20であり、
前記疎水性剤(C)は、SP値がカチオン性エポキシ樹脂(A)に対し0.6~1.0低い化合物であって、その含有量が、前記カチオン性エポキシ樹脂(A)と前記ブロックポリイソシアネート硬化剤(B)との合計量に対して0.2~5質量%であり、
前記粘度調整剤(D)は、樹脂粒子であって、その含有量が、前記カチオン性エポキシ樹脂(A)と前記ブロックポリイソシアネート硬化剤(B)と前記疎水性剤(C)との合計量に対して3~10質量%であり、
前記カチオン電着塗料組成物のクーロン効率が、2.0~2.5mg/(μm・C)であり、
前記疎水性剤(C)が非架橋アクリル樹脂であり、
前記電圧の昇圧速度が30~70V/10secである、
電着塗膜形成方法。 - 前記被塗物が複数の鋼板を接続して形成された構造物であり、該複数の鋼板の接続部が、接続のために重ねられた鋼板と鋼板の間に隙間を有しているものである、請求項3に記載の電着塗膜形成方法。
- 前記隙間の最も狭い部分の間隔が300μm以下である請求項4に記載の電着塗膜形成方法。
- 前記カチオン性エポキシ樹脂(A)のSP値が11.2~11.6であり、前記疎水性剤(C)のSP値が10.2~10.6である請求項3~5のいずれか一項に記載の電着塗膜形成方法。
- 前記粘度調整剤(D)は、平均粒子径が50~200nmである架橋樹脂粒子である、請求項3~6のいずれか一項に記載の電着塗膜形成方法。
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
MX2013012988A MX346078B (es) | 2011-05-12 | 2012-05-11 | Composicion de pintura por electrodeposicion cationica que incluso es capaz de recubrir secciones que tienen espacios libres estrechos, y metodo de formacion de pelicula de pintura por electrodeposicion que la utiliza. |
BR112013028628A BR112013028628A2 (pt) | 2011-05-12 | 2012-05-11 | composição de pintura por eletrodeposição catiônica capaz de ser pintada mesmo em uma porção de espaço estreito, e filme de revestimento por eletrodeposição usando a mesma |
EP12783059.4A EP2708583B1 (en) | 2011-05-12 | 2012-05-11 | Cationic electrodeposition paint composition capable even of coating sections having narrow clearance, and electrodeposition paint-film formation method using same |
CN201280023066.1A CN103635547B (zh) | 2011-05-12 | 2012-05-11 | 可涂装至狭窄的间隙部的阳离子电沉积涂料组合物及使用其的电沉积涂膜形成方法 |
US14/116,588 US9157163B2 (en) | 2011-05-12 | 2012-05-11 | Cationic electrodeposition paint composition paintable even on narrow-clearance portion, and electrodeposition coating film using the same |
RU2013155196/05A RU2561080C2 (ru) | 2011-05-12 | 2012-05-11 | Композиция для окрашивания катионным электроосаждением, пригодная для окрашивания даже участков узких зазоров, и покровная пленка, нанесенная электроосаждением при ее применении |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011107304A JP5769236B2 (ja) | 2011-05-12 | 2011-05-12 | 狭いクリアランス部にまで塗装可能なカチオン電着塗料組成物及びそれを用いた電着塗膜形成方法 |
JP2011-107304 | 2011-05-12 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012153850A1 true WO2012153850A1 (ja) | 2012-11-15 |
Family
ID=47139323
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2012/062195 WO2012153850A1 (ja) | 2011-05-12 | 2012-05-11 | 狭いクリアランス部にまで塗装可能なカチオン電着塗料組成物及びそれを用いた電着塗膜形成方法 |
Country Status (8)
Country | Link |
---|---|
US (1) | US9157163B2 (ja) |
EP (1) | EP2708583B1 (ja) |
JP (1) | JP5769236B2 (ja) |
CN (1) | CN103635547B (ja) |
BR (1) | BR112013028628A2 (ja) |
MX (1) | MX346078B (ja) |
RU (1) | RU2561080C2 (ja) |
WO (1) | WO2012153850A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103319689A (zh) * | 2013-06-24 | 2013-09-25 | 浩力森涂料(上海)有限公司 | 一种高泳透力阴极电泳涂料用乳液树脂及其制备方法 |
WO2015146480A1 (ja) * | 2014-03-25 | 2015-10-01 | 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 |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP7016224B2 (ja) * | 2017-05-11 | 2022-02-04 | 日本パーカライジング株式会社 | 複合体、水性樹脂組成物及び塗料 |
WO2019070146A1 (ru) * | 2017-10-04 | 2019-04-11 | Общество С Ограниченной Ответственностью "Рустек" | Лакокрасочная композиция для получения тонких покрытий методом катодного электроосаждения |
WO2019209266A1 (en) * | 2018-04-24 | 2019-10-31 | Hewlett-Packard Development Company, L.P. | Metal and polymer coating of metal substrates |
CN109023485B (zh) * | 2018-08-23 | 2020-10-27 | 深圳和而泰智能控制股份有限公司 | 一种铝合金压铸件的表面处理方法 |
CN117460792A (zh) * | 2021-06-24 | 2024-01-26 | Ppg工业俄亥俄公司 | 可电沉积的涂层组合物 |
JP7198961B1 (ja) * | 2022-08-09 | 2023-01-04 | 日本ペイントマリン株式会社 | 下塗り用塗料組成物及び塗膜 |
Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS544978B2 (ja) | 1975-08-01 | 1979-03-12 | ||
JPS5634186B2 (ja) | 1976-01-14 | 1981-08-08 | ||
JPS6363761A (ja) * | 1986-09-04 | 1988-03-22 | Nippon Paint Co Ltd | 電着塗料組成物 |
JPH02282499A (ja) * | 1989-04-25 | 1990-11-20 | Kansai Paint Co Ltd | カチオン電着塗装方法 |
JPH0625567A (ja) | 1992-07-06 | 1994-02-01 | Nissan Motor Co Ltd | カチオン電着塗料組成物 |
JPH07286297A (ja) * | 1994-04-20 | 1995-10-31 | Nippon Paint Co Ltd | 電着塗装方法 |
JPH09195091A (ja) * | 1996-01-19 | 1997-07-29 | Toyota Motor Corp | 電着塗装方法 |
JP2000128959A (ja) | 1998-10-27 | 2000-05-09 | Nippon Paint Co Ltd | オキサゾリドン環含有エポキシ樹脂 |
JP2002212488A (ja) * | 2001-01-23 | 2002-07-31 | Nippon Paint Co Ltd | 架橋樹脂粒子を含有するカチオン電着塗料組成物 |
JP2006348316A (ja) | 2005-06-13 | 2006-12-28 | Nippon Paint Co Ltd | 電着塗膜形成方法 |
JP2009235350A (ja) | 2008-03-28 | 2009-10-15 | Nippon Paint Co Ltd | カチオン電着塗料組成物 |
JP2010037481A (ja) * | 2008-08-07 | 2010-02-18 | Nippon Paint Co Ltd | カチオン電着塗料組成物およびカチオン電着塗装方法 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS544978A (en) | 1977-06-14 | 1979-01-16 | Mitsubishi Gas Chem Co Inc | Device for solvent removal |
AU590960B2 (en) | 1986-09-04 | 1989-11-23 | Nippon Paint Co., Ltd. | Electrodeposition coating composition |
JPH10204337A (ja) * | 1997-01-23 | 1998-08-04 | Nippon Paint Co Ltd | カチオン電着塗料組成物 |
JP3362179B2 (ja) | 1998-10-22 | 2003-01-07 | 新潟大学長 | コンクリート系建設材料のリサイクル方法 |
CN1483776A (zh) * | 2002-09-19 | 2004-03-24 | 日本油漆株式会社 | 用于电子器件的阳离子型电沉积涂敷组合物 |
US7576160B2 (en) * | 2005-05-06 | 2009-08-18 | Ppg Industries Ohio, Inc. | Electrocoat composition imparting sweat resistance and methods for using the same |
US20070015873A1 (en) * | 2005-07-13 | 2007-01-18 | Fenn David R | Electrodepositable aqueous resinous dispersions and methods for their preparation |
-
2011
- 2011-05-12 JP JP2011107304A patent/JP5769236B2/ja active Active
-
2012
- 2012-05-11 MX MX2013012988A patent/MX346078B/es active IP Right Grant
- 2012-05-11 RU RU2013155196/05A patent/RU2561080C2/ru not_active IP Right Cessation
- 2012-05-11 BR BR112013028628A patent/BR112013028628A2/pt not_active IP Right Cessation
- 2012-05-11 EP EP12783059.4A patent/EP2708583B1/en active Active
- 2012-05-11 WO PCT/JP2012/062195 patent/WO2012153850A1/ja active Application Filing
- 2012-05-11 CN CN201280023066.1A patent/CN103635547B/zh active Active
- 2012-05-11 US US14/116,588 patent/US9157163B2/en active Active
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS544978B2 (ja) | 1975-08-01 | 1979-03-12 | ||
JPS5634186B2 (ja) | 1976-01-14 | 1981-08-08 | ||
JPS6363761A (ja) * | 1986-09-04 | 1988-03-22 | Nippon Paint Co Ltd | 電着塗料組成物 |
JPH02282499A (ja) * | 1989-04-25 | 1990-11-20 | Kansai Paint Co Ltd | カチオン電着塗装方法 |
JPH0625567A (ja) | 1992-07-06 | 1994-02-01 | Nissan Motor Co Ltd | カチオン電着塗料組成物 |
JPH07286297A (ja) * | 1994-04-20 | 1995-10-31 | Nippon Paint Co Ltd | 電着塗装方法 |
JPH09195091A (ja) * | 1996-01-19 | 1997-07-29 | Toyota Motor Corp | 電着塗装方法 |
JP2000128959A (ja) | 1998-10-27 | 2000-05-09 | Nippon Paint Co Ltd | オキサゾリドン環含有エポキシ樹脂 |
JP2002212488A (ja) * | 2001-01-23 | 2002-07-31 | Nippon Paint Co Ltd | 架橋樹脂粒子を含有するカチオン電着塗料組成物 |
JP2006348316A (ja) | 2005-06-13 | 2006-12-28 | Nippon Paint Co Ltd | 電着塗膜形成方法 |
JP2009235350A (ja) | 2008-03-28 | 2009-10-15 | Nippon Paint Co Ltd | カチオン電着塗料組成物 |
JP2010037481A (ja) * | 2008-08-07 | 2010-02-18 | Nippon Paint Co Ltd | カチオン電着塗料組成物およびカチオン電着塗装方法 |
Non-Patent Citations (2)
Title |
---|
See also references of EP2708583A4 * |
SUH, CLARKE, J.P.S. A-1, no. 5, 1967, pages 1671 - 1681 |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103319689A (zh) * | 2013-06-24 | 2013-09-25 | 浩力森涂料(上海)有限公司 | 一种高泳透力阴极电泳涂料用乳液树脂及其制备方法 |
CN103319689B (zh) * | 2013-06-24 | 2015-11-18 | 浩力森涂料(上海)有限公司 | 一种高泳透力阴极电泳涂料用乳液树脂及其制备方法 |
WO2015146480A1 (ja) * | 2014-03-25 | 2015-10-01 | 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 |
JP2015183106A (ja) * | 2014-03-25 | 2015-10-22 | 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 |
US11041079B2 (en) | 2014-03-25 | 2021-06-22 | Nippon Paint Automotive Coatings Co., Ltd. | Electrodeposition coating composition and electrodeposition coating method |
Also Published As
Publication number | Publication date |
---|---|
EP2708583A1 (en) | 2014-03-19 |
JP2012236928A (ja) | 2012-12-06 |
MX346078B (es) | 2017-03-07 |
US20140124375A1 (en) | 2014-05-08 |
MX2013012988A (es) | 2013-12-06 |
RU2561080C2 (ru) | 2015-08-20 |
JP5769236B2 (ja) | 2015-08-26 |
CN103635547A (zh) | 2014-03-12 |
US9157163B2 (en) | 2015-10-13 |
RU2013155196A (ru) | 2015-06-20 |
BR112013028628A2 (pt) | 2017-12-05 |
CN103635547B (zh) | 2017-03-08 |
EP2708583A4 (en) | 2015-08-05 |
EP2708583B1 (en) | 2017-03-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5769236B2 (ja) | 狭いクリアランス部にまで塗装可能なカチオン電着塗料組成物及びそれを用いた電着塗膜形成方法 | |
US20050282936A1 (en) | Cationic electrodeposition coating composition | |
EP2752467B1 (en) | Method for preparing emulsion resin composition for cationic electrodeposition coating | |
JP4060620B2 (ja) | 無鉛性カチオン電着塗料を用いる電着塗装方法 | |
JP2009235350A (ja) | カチオン電着塗料組成物 | |
US6136895A (en) | Cationic electrocoating composition | |
JP2001192611A (ja) | カチオン電着塗料組成物 | |
JP2010095668A (ja) | カチオン性電着塗料組成物 | |
JP2010037481A (ja) | カチオン電着塗料組成物およびカチオン電着塗装方法 | |
US20070244226A1 (en) | Cationic Electrodeposition Coating Composition | |
JP2008037889A (ja) | 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 | |
JP2002356647A (ja) | 無鉛性カチオン電着塗料組成物及び塗装方法 | |
JP2002294141A (ja) | カチオン電着塗料組成物 | |
JP2008106134A (ja) | カチオン電着塗料組成物およびその応用 | |
JP2000336287A (ja) | 低光沢鉛フリーカチオン電着塗料組成物、塗膜形成方法および塗装物 | |
JP2002356646A (ja) | 架橋樹脂粒子を含有する無鉛性カチオン電着塗料組成物 | |
JP2009235351A (ja) | カチオン電着塗料組成物 | |
JP2002356645A (ja) | 無鉛性カチオン電着塗料組成物 | |
JP4326351B2 (ja) | カチオン電着塗膜の形成方法 | |
JP2002285391A (ja) | 電着塗装方法 | |
JP2002285392A (ja) | 電着塗装方法 | |
JP2004123942A (ja) | カチオン電着塗料組成物 | |
JP2002294146A (ja) | 無鉛性カチオン電着塗料組成物 | |
JP2005200506A (ja) | カチオン電着塗料組成物 | |
JP2015193684A (ja) | カチオン電着塗料組成物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 12783059 Country of ref document: EP Kind code of ref document: A1 |
|
DPE1 | Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101) | ||
REEP | Request for entry into the european phase |
Ref document number: 2012783059 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: MX/A/2013/012988 Country of ref document: MX Ref document number: 2012783059 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14116588 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 2013155196 Country of ref document: RU Kind code of ref document: A |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112013028628 Country of ref document: BR |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01E Ref document number: 112013028628 Country of ref document: BR |
|
ENP | Entry into the national phase |
Ref document number: 112013028628 Country of ref document: BR Kind code of ref document: A2 Effective date: 20131106 |