WO2021006220A1 - カチオン電着塗料組成物 - Google Patents

カチオン電着塗料組成物 Download PDF

Info

Publication number
WO2021006220A1
WO2021006220A1 PCT/JP2020/026266 JP2020026266W WO2021006220A1 WO 2021006220 A1 WO2021006220 A1 WO 2021006220A1 JP 2020026266 W JP2020026266 W JP 2020026266W WO 2021006220 A1 WO2021006220 A1 WO 2021006220A1
Authority
WO
WIPO (PCT)
Prior art keywords
parts
electrodeposition coating
resin
coating composition
pigment
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2020/026266
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
菜見子 坂井
誠之 小谷
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Paint Automotive Coatings Co Ltd
Original Assignee
Nippon Paint Automotive Coatings 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 Automotive Coatings Co Ltd filed Critical Nippon Paint Automotive Coatings Co Ltd
Priority to CN202080049719.8A priority Critical patent/CN114040947B/zh
Priority to MX2021015951A priority patent/MX2021015951A/es
Priority to EP20836845.6A priority patent/EP3998316A4/en
Priority to US17/624,404 priority patent/US20220332960A1/en
Publication of WO2021006220A1 publication Critical patent/WO2021006220A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—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
    • C09D5/448—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications characterised by the additives used
    • 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
    • C09D5/4473—Mixture of polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • 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
    • 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
    • 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
    • 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
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences

Definitions

  • the present invention relates to a cationic electrodeposition coating composition.
  • a plurality of coating films having various roles are formed on the surface of an object to be coated such as a metal base material.
  • the coating film protects the object to be coated and at the same time gives the object to be coated a beautiful appearance.
  • an electrodeposition coating film formed by electrodeposition coating is widely used as a coating film for imparting corrosion resistance to an object to be coated. According to electrodeposition coating, even an object to be coated having a complicated shape can be coated in detail. Further, according to electrodeposition coating, the object to be coated can be automatically and continuously coated. Therefore, electrodeposition coating has been widely put into practical use as an undercoat coating method for a large and complicated object to be coated, such as an automobile body. As such electrodeposition coating, electrodeposition coating using a cationic electrodeposition coating composition is widely used.
  • the coating film is also required to have a good surface condition.
  • One of the factors that reduce the smoothness of the coating film is, for example, a phenomenon called repellent.
  • the term "hajiki” as used herein refers to surface defects (dents / holes) on the surface of the coating film that occur in a series of coating / drying steps.
  • the components (causative substances) that cause these surface defects are often unintentionally brought into the coating composition from, for example, the raw materials of the coating composition, the manufacturing equipment, the container, the base material to be coated, and the like. And it is difficult to completely eliminate such causative substances from the coating composition.
  • Patent Document 1 describes a pigment dispersion paste for electrodeposition coatings, which contains a pigment dispersion resin (A), cellulose (B), extender pigment (C) and water.
  • the extender pigment (C) has a zeta potential in the range of -10 mV to +50 mV, and the pigment dispersion paste contains cellulose (B) and the extender per 100 parts by mass of the pigment dispersion resin (A) in terms of solid content.
  • the pigment dispersion paste is described according to claim 1, wherein the pigment (C) is contained in a ratio of 0.1 to 25 parts by mass and 80 to 800 parts by mass, respectively.
  • Patent Document 1 describes that the inclusion of this pigment-dispersed paste makes it difficult for defects such as repellents and lumps to occur when used after stirring, circulation, etc. have been stopped for a long period of time.
  • Patent Document 1 The invention described in Patent Document 1 is an invention that attempts to prevent the occurrence of cissing by using a specific extender pigment (C).
  • a specific pigment as an essential component, the design range such as the color tone and the physical characteristics of the coating film of the electrodeposition coating composition may be limited. Further, in recent years, there is a tendency that a higher level of repellency prevention performance is required.
  • An object of the present invention is to solve the above technical problems, and an object of the present invention is to provide an electrodeposition coating composition having a higher level of repellency prevention performance.
  • a cationic electrodeposition coating composition containing a coating film-forming resin (A), a metal compound (B) containing a trivalent metal element, and a silicone compound (C).
  • the content of the metal compound (B) is 0.03 parts by mass or more and less than 4 parts by mass in terms of metal elements with respect to 100 parts by mass of the resin solid content of the coating film-forming resin (A).
  • the content of the silicone compound (C) is 0.005 parts by mass or more and 4.5 parts by mass or less with respect to 100 parts by mass of the resin solid content of the coating film-forming resin (A).
  • the silicone compound (C) is at least one selected from the group consisting of a polyether-modified silicone compound (C-1), a polyester-modified silicone compound (C-2), and a polyacrylic-modified silicone compound (C-3).
  • the cationic electrodeposition coating composition according to any one of the above [1] to [3].
  • the cationic electrodeposition coating composition of the present invention has good anti-repellency performance.
  • a cured electrodeposition coating film having a good coating film appearance can be formed.
  • the cationic electrodeposition coating composition contains a coating film-forming resin (A), a metal compound (B) containing a trivalent metal element, and a silicone compound (C).
  • A coating film-forming resin
  • B metal compound
  • C silicone compound
  • the cationic electrodeposition coating composition contains a coating film forming resin (A).
  • the coating film-forming resin (A) contained in the cationic electrodeposition coating composition preferably contains a resin emulsion containing an aminized resin and a curing agent.
  • Amine resin is a coating film forming resin that constitutes an electrodeposition coating film.
  • an amine-modified epoxy resin obtained by modifying the oxylan ring in the resin skeleton with an organic amine compound is preferable.
  • an amine-modified epoxy resin is prepared by opening the oxylan ring in the starting material resin molecule by reaction with an amine such as a primary amine, a secondary amine or a tertiary amine and / or an acid salt thereof.
  • a typical example of a starting material resin is a polyphenol polyglycidyl ether type epoxy resin which is a reaction product of a polycyclic phenol compound such as bisphenol A, bisphenol F, bisphenol S, phenol novolac, and cresol novolac with epichlorohydrin.
  • a polycyclic phenol compound such as bisphenol A, bisphenol F, bisphenol S, phenol novolac, and cresol novolac with epichlorohydrin.
  • an oxazolidone ring-containing epoxy resin described in JP-A-5-306327 can be mentioned.
  • These epoxy resins can be prepared by reacting a diisocyanate compound or a bisurethane compound obtained by blocking the isocyanate group of the diisocyanate compound with a lower alcohol such as methanol or ethanol with epichlorohydrin.
  • the starting material resin can be used by extending the chain with a bifunctional polyester polyol, a polyether polyol, a bisphenol, a dibasic carboxylic acid, or the like before the ring-opening reaction of the oxylan ring with amines.
  • bisphenols may be used to extend the chain before the ring-opening reaction of the oxylan ring with amines.
  • 2-ethylhexanol, nonylphenol, ethylene for some oxylan rings for the purpose of adjusting the molecular weight or amine equivalent, improving the thermal flow property, etc. before the ring opening reaction of the oxylan ring with amines.
  • Monohydroxy compounds such as glycol mono-2-ethylhexyl ether, ethylene glycol mono n-butyl ether and propylene glycol mono-2-ethylhexyl ether, and monocarboxylic acid compounds such as octyl acid may be added.
  • Examples of amines that can be used to open the oxylan ring and introduce an amino group include butylamine, octylamine, diethylamine, dibutylamine, methylbutylamine, monoethanolamine, diethanolamine, N-methylethanolamine, triethylamine. , N, N-dimethylbenzylamine, N, N-dimethylethanolamine and other primary amines, secondary amines or tertiary amines and / or acid salts thereof. Further, a ketimine block primary amino group-containing secondary amine such as aminoethylethanolamine methylisobutylketimine and diethylenetriamine diketimine can also be used. These amines need to react with the oxylan ring in at least equivalent amounts in order to open all the oxylan rings.
  • the number average molecular weight of the aminized resin is preferably 1,000 or more and 5,000 or less.
  • the number average molecular weight is 1,000 or more, the physical properties such as solvent resistance and corrosion resistance of the obtained cured electrodeposition coating film are improved.
  • the number average molecular weight is 5,000 or less, the viscosity of the aminated resin can be easily adjusted to enable smooth synthesis, and the emulsified dispersion of the obtained aminated resin can be easily handled.
  • the number average molecular weight of the aminized resin is more preferably in the range of 1,600 or more and 3,200 or less.
  • the number average molecular weight is a polystyrene-equivalent number average molecular weight measured by gel permeation chromatography (GPC).
  • the amine value of the amination resin is preferably in the range of 20 mgKOH / g or more and 100 mgKOH / g or less.
  • the amine value of the aminized resin is 20 mgKOH / g or more, the emulsion dispersion stability of the aminated resin in the electrodeposition coating composition becomes good.
  • the amine value is 100 mgKOH / g or less, the amount of amino groups in the cured electrodeposition coating film becomes appropriate, and there is no possibility that the water resistance of the coating film is lowered.
  • the amine value of the amination resin is more preferably in the range of 20 mgKOH / g or more and 80 mgKOH / g or less.
  • the hydroxyl value of the aminized resin is preferably in the range of 50 mgKOH / g or more and 400 mgKOH / gmgKOH / g or less.
  • the hydroxyl value of the aminized resin is more preferably in the range of 100 mgKOH / g or more and 300 mgKOH / g or less.
  • the number average molecular weight is 1,000 or more and 5,000 or less
  • the amine value is 20 mgKOH / g or more and 100 mgKOH / g or less
  • the hydroxyl value is 50 mgKOH / g or more and 400 mgKOH /.
  • an aminized resin having a different amine value and / or hydroxyl value may be used in combination, if necessary.
  • the average amine value and average hydroxyl value calculated based on the mass ratio of the aminating resin used are within the above numerical range. preferable.
  • the aminating resin to be used in combination includes an amine resin having an amine value of 20 mgKOH / g or more and 50 mgKOH / g or less and a hydroxyl value of 50 mgKOH / g or more and 300 mgKOH / g or less, and an amine value of 50 mgKOH / g.
  • Aminated resins having g or more and 200 mgKOH / g or less and a hydroxyl value of 200 mgKOH / g or more and 500 mgKOH / g or less are preferable.
  • the core portion of the emulsion becomes more hydrophobic and the shell portion becomes hydrophilic, so that there is an advantage that excellent corrosion resistance can be imparted.
  • the aminized resin may contain an amino group-containing acrylic resin, an amino group-containing polyester resin, and the like, if necessary.
  • the resin emulsion contains a hardener.
  • a blocked isocyanate curing agent is preferably used.
  • the blocked isocyanate curing agent can be prepared by blocking the polyisocyanate with a blocking agent.
  • polyisocyanates examples include aliphatic diisocyanates such as hexamethylene diisocyanate (including trimer), tetramethylene diisocyanate and trimethylhexamethylene diisocyanate; and fats such as isophorone diisocyanate and 4,4'-methylenebis (cyclohexylisocyanate).
  • aliphatic diisocyanates such as hexamethylene diisocyanate (including trimer), tetramethylene diisocyanate and trimethylhexamethylene diisocyanate
  • fats such as isophorone diisocyanate and 4,4'-methylenebis (cyclohexylisocyanate).
  • Cyclic polyisocyanate aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate; modified products of these diisocyanates (urethane products, carbodiimide, uretdione, uretonimine, burette and / or isocyanurate modification Things, etc.).
  • aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate
  • modified products of these diisocyanates urethane products, carbodiimide, uretdione, uretonimine, burette and / or isocyanurate modification Things, etc.
  • blocking agents are monohydric alkyl (or aromatic) alcohols such as n-butanol, n-hexyl alcohol, 2-ethylhexanol, lauryl alcohol, phenolcarbinol, methylphenylcarbinol; ethylene glycol monohexyl.
  • Cellosolves such as ether, ethylene glycol mono2-ethylhexyl ether; polyether-type both-terminal diols such as polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol phenol; ethylene glycol, propylene glycol, 1,4-butanediol, etc.
  • Polyester-type double-ended polyols obtained from diols and dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, suberic acid, and sebacic acid; phenols such as para-t-butylphenol and cresol; dimethylketooxime and methylethylketooxime , Oxims such as methylisobutylketooxime, methylamylketooxym, cyclohexanone oxime; and lactams typified by ⁇ -caprolactam and ⁇ -butyrolactam are preferably used.
  • dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, suberic acid, and sebacic acid
  • phenols such as para-t-butylphenol and cresol
  • dimethylketooxime and methylethylketooxime Oxims such as methylisobutylketooxime, methylamy
  • the blocking rate of the blocked isocyanate curing agent is preferably 100%. This has the advantage that the storage stability of the electrodeposited coating composition is improved.
  • the blocked isocyanate curing agent it is preferable to use a curing agent prepared by blocking an aliphatic diisocyanate with a blocking agent and a curing agent prepared by blocking an aromatic diisocyanate with a blocking agent.
  • the blocked isocyanate curing agent preferentially reacts with the primary amine of the amination resin, and further reacts with the hydroxyl group to cure.
  • the curing agent at least one curing agent selected from the group consisting of organic curing agents such as melamine resin or phenol resin, silane coupling agents, and metal curing agents may be used in combination with the blocked isocyanate curing agent.
  • a resin emulsion is prepared by dissolving each of an aminized resin and a curing agent in an organic solvent to prepare a solution, mixing these solutions, and then neutralizing with a neutralizing acid.
  • the neutralizing acid include organic acids such as methanesulfonic acid, sulfamic acid, lactic acid, dimethylolpropionic acid, formic acid and acetic acid.
  • the content of the curing agent is sufficient to give a good cured coating by reacting with an active hydrogen-containing functional group such as a primary amino group, a secondary amino group or a hydroxyl group in the aminating resin during curing. Needed.
  • the content of the curing agent is preferably 90/10 to 50/50, more preferably 80/20 to 65/35 in terms of the solid content mass ratio (amined resin / curing agent) of the aminating resin and the curing agent. The range.
  • the solid content of the resin emulsion is usually 25% by mass or more and 50% by mass or less, and particularly preferably 35% by mass or more and 45% by mass or less with respect to the total amount of the resin emulsion.
  • the "solid content of the resin emulsion” means the masses of all the components contained in the resin emulsion that remain solid even after the removal of the solvent. Specifically, it means the total mass of the aminating resin, the curing agent and other solid components added as needed in the resin emulsion.
  • the neutralizing acid is preferably used in an amount of 10% or more and 100% or less, and is used in an amount of 20% or more and 70% or less as the equivalent ratio of the neutralizing acid to the equivalent of the amino group contained in the amine resin. Is more preferable.
  • the ratio of the equivalent of the neutralizing acid to the equivalent of the amino group of the aminated resin is defined as the neutralization rate.
  • the coating film-forming resin (A) when the coating film-forming resin (A) contains a resin emulsion containing an aminized resin and a curing agent, 100 parts by mass of the resin solid content of the coating film-forming resin means that the total of these resin solids is 100 mass by mass. It means that it is a department.
  • 100 parts by mass of the resin solid content contained in the coating film-forming resin (A) is the plurality of types of resin solids. Means that the total of is 100 parts by mass.
  • coating film-forming resin (A) examples include acrylic resin, polyester resin, urethane resin, butadiene resin, phenol resin, and xylene resin.
  • the cationic electrodeposition coating composition contains a metal compound (B) containing a trivalent metal element.
  • a metal compound (B) containing a trivalent metal element means a metal element that becomes a trivalent cation.
  • the trivalent metal element include Y, La, Ce, Nd, Pr, Yb, Bi and the like. These may be used alone or in combination of two or more. Examples of the form of the metal compound include metal oxides and metal hydroxides.
  • the metal element contained in the metal compound (B) is preferably one or more selected from the group consisting of Y, La, Ce, Nd and Bi.
  • the cationic electrodeposition coating composition contains the metal compound (B), there is an advantage that good rust prevention and curability can be obtained. Further, in the cationic electrodeposition coating composition, there is an advantage that good repellency prevention performance is achieved by using the metal compound (B) and the silicone compound (C) in combination.
  • the metal compound (B) contains a bismuth compound
  • good effect performance can be imparted to the cationic electrodeposition coating composition.
  • the bismuth compound in the cationic electrodeposition coating composition, it is not necessary to use a lead compound, an organic tin compound or the like as a curing catalyst. This makes it possible to prepare an electrodeposition coating composition that is substantially free of any tin compound or lead compound.
  • the content of the metal compound (B) is 0.03 parts by mass or more and less than 4 parts by mass in terms of metal elements with respect to 100 parts by mass of the resin solid content contained in the cationic electrodeposition coating composition. If the content of the metal compound (B) is less than 0.03 parts by mass, the balance between the appearance of the obtained cured electrodeposition coating film and the performance of preventing repellency may be lost. Further, when the content of the metal compound (B) is 4 parts by mass or more, the appearance of the obtained cured electrodeposition coating film may be inferior.
  • the content of the metal compound (B) is preferably 0.04 parts by mass or more and 3.8 parts by mass or less, and more preferably 0.05 parts by mass or more and 3.5 parts by mass or less.
  • Silicone compound (C) The cationic electrodeposition coating composition contains a silicone compound (C).
  • the SP value of the silicone compound (C) is preferably more than 10.5 and 15.0 or less.
  • the cationic electrodeposition coating composition contains both the metal compound (B) and the silicone compound (C) within a specific content range.
  • good repelling prevention property can be exhibited even when the mechanism in which the oil is present is different. Therefore, for example, good anti-repellency can be exhibited against oils derived from devices used in drying and curing steps such as indirect furnaces and drying furnaces, that is, oils that can be mixed after painting and before curing. ..
  • oils that may be mixed after painting and before curing may be mixed in a high temperature state such as near the baking temperature.
  • the coating composition contains oil, good anti-repellency can be exhibited even if the coating film is formed under the condition that the oil can remain on the object to be coated.
  • the obtained electrodeposition coating film can show a good appearance, and for example, the generation of lumps (small protrusion-like impurities) can be suppressed. Further, it can have a good coating film appearance such as having a uniform coating film surface and not causing coating unevenness.
  • the SP value of the silicone compound (C) is preferably more than 10.5 and 15.0 or less.
  • the SP value is more preferably 11.0 or more and 15.0 or less, and further preferably 12.0 or more and 15.0 or less.
  • the SP value is particularly preferably 12.3 or more and less than 15.0, and particularly preferably 12.5 or more and less than 15.0.
  • the SP value of the silicone compound (C) When the SP value of the silicone compound (C) is within such a range, the appearance of the obtained coating film is not impaired, and good anti-repellency can be obtained even if the oil invasion route is various conditions. There is an advantage to be. Further, for example, it can exhibit good adhesion to a top coat film and the like. Further, when the SP value of the silicone compound (C) is within such a range, there is an advantage that the repellency prevention performance can be satisfactorily secured, and moreover, good paint stability can be obtained. Although it should not be interpreted only in a specific theory, the SP value of the silicone compound (C) within such a range ensures good anti-repellency and appearance without impairing paint stability. It is considered that it is compatible with.
  • the SP value is an abbreviation for solubility parameter (solubility parameter), which is a measure of solubility.
  • solubility parameter is a measure of solubility. The larger the SP value, the higher the polarity, and conversely, the smaller the value, the lower the polarity.
  • the SP value can be measured by the following method [References: SUH, CLARKE, J. et al. P. S. A-1, 5, 1671 to 1681 (1967)].
  • an organic solvent is weighed in a 100 ml beaker, 10 ml of acetone is added using a whole pipette, and the mixture is dissolved by a magnetic stirrer.
  • a poor solvent is added dropwise to this sample at a measurement temperature of 20 ° C. using a 50 ml burette, and the point at which turbidity occurs is defined as the amount of addition.
  • the poor solvent ion-exchanged water is used as the high SP poor solvent, and n-hexane is used as the low SP poor solvent, and the turbidity point is measured.
  • the SP value ⁇ of the organic solvent is given by the following formula.
  • the SP value of the silicone compound (C) is the solid content mass ratio in the silicone compound (C) component using the SP value of each compound. It can be obtained by calculating the average value based on.
  • the cationic electrodeposition coating composition contains 0.005 parts by mass or more and 4.5 parts by mass or less of the silicone compound (C) with respect to 100 parts by mass of the resin solid content of the coating film forming resin (A).
  • the content of the silicone compound (C) is preferably 0.006 parts by mass or more and 4.0 parts by mass or less, and more preferably 0.008 parts by mass or more and 3.8 parts by mass or less.
  • the amount of the silicone compound (C) is within such a range, the appearance of the obtained coating film is not impaired, and various repellents having different mechanisms shown in the mixed oil repellent evaluation, the flowing oil repellent evaluation, etc. It also has good anti-repellency. Further, there is an advantage that good adhesion can be exhibited with various coating films such as a top coating film.
  • the silicone compound (C) having the above-mentioned predetermined SP value has advantages that it can exist stably in an aqueous system, can be dissolved or dispersed in an aqueous solvent, and can be easily dispersed in water by itself.
  • the fact that the silicone compound (C) can be dissolved or dispersed in an aqueous solvent means that the silicone compound (C) is mixed with the aqueous solvent in a predetermined amount shown in the present disclosure at room temperature. In the case, it means that it can be easily dissolved or uniformly dispersed.
  • the fact that it is easily dispersed in water by itself means that the silicone compound (C) can be uniformly dispersed in an aqueous solvent at room temperature without using a dispersant, a surfactant or the like.
  • the silicone compound (C) Since the silicone compound (C) has such properties, it can have good paint stability, for example, it has stability in an aqueous system. Moreover, in the production of the cationic coating composition, the silicone compound (C) can be dispersed in an aqueous solvent without being diluted with a solvent, so that the burden on the environment can be reduced.
  • the silicone compound (C) has a polysiloxane as the main skeleton.
  • polysiloxane has 3 or more and 20 or less Si atoms in the molecule, for example, 3 or more and 10 or less.
  • the silicone compound (C) has polydimethylsiloxane as the main skeleton.
  • the silicone compound (C) is at least selected from the group consisting of the polyether-modified silicone compound (C-1), the polyester-modified silicone compound (C-2) and the polyacrylic-modified silicone compound (C-3). There is one.
  • the cationic electrodeposition coating composition of the present disclosure may contain these modified silicone compounds alone or in combination. By including such a silicone compound (C), the cationic electrodeposition coating composition of the present disclosure can be provided with both better anti-repellency and better coating film appearance, and moreover. It can show good paint stability.
  • the silicone compound (C) is at least one selected from the polyether-modified silicone compound (C-1), the polyester-modified silicone compound (C-2) and the polyacrylic-modified silicone compound (C-3). And include.
  • the silicone compound (C) can have more stable hydration property.
  • the cationic electrodeposition coating composition of the present disclosure having such a silicone compound (C) can have excellent anti-repellency.
  • better paint stability can be exhibited.
  • the polyether-modified silicone compound (C-1) examples include compounds in which a polyether chain is introduced into the terminal and / or side chain of the polysiloxane.
  • the polysiloxane may further have a substituent other than the polyether chain.
  • the polyether-modified silicone compound (C-1) is a compound in which a polyether chain is introduced into a side chain of a polysiloxane, for example, polydimethylsiloxane.
  • the cationic electrodeposition coating compositions of the present disclosure have better anti-repellency, better coating appearance, eg, better coating smoothness and coating. It is possible to show effects such as no unevenness. It can also show better paint stability. Further, there is an advantage that the adhesion between the electrodeposition coating film formed from the cationic electrodeposition coating composition and the topcoat coating film or the like is improved.
  • polyester-modified silicone compound (C-2) examples include compounds in which a polyester chain is introduced into the terminal and / or side chain of the polysiloxane.
  • the polysiloxane may further have a substituent other than the polyester chain.
  • the polyester-modified silicone compound (C-2) is a compound in which a polyester chain is introduced into a side chain of polysiloxane, for example, polydimethylsiloxane.
  • Examples of the polyacrylic-modified silicone compound (C-3) include compounds in which a polyacrylic chain is introduced into the terminal and / or side chain of the polysiloxane.
  • the polysiloxane may further have a substituent other than the polyacrylic chain.
  • the polyacrylic modified silicone compound (C-3) is a compound in which a polyacrylic chain is introduced into a side chain of polysiloxane, for example, polydimethylsiloxane.
  • the cationic electrodeposition coating composition of the present disclosure can exhibit better anti-repellency and coating film appearance. It can also show better paint stability. Further, there is an advantage that the adhesion between the electrodeposition coating film formed from the cationic electrodeposition coating composition and the topcoat coating film or the like is improved.
  • the click electrodeposition coating composition may contain a pigment in addition to the above components.
  • the cationic electrodeposition coating composition contains a pigment
  • the pigment dispersion paste can be prepared by a method known to those skilled in the art.
  • Examples 1 of the preparation of such a pigment-dispersed paste include the following embodiments 1 to 3.
  • the pigment dispersion paste contains a metal compound (B), a pigment dispersion resin and a pigment;
  • the pigment dispersion paste is An embodiment prepared by mixing the metal compound (B) and the pigment-dispersed resin, and mixing the obtained mixture, the pigment-dispersed resin, and the pigment.
  • the pigment dispersion paste contains a metal compound (B), a pigment dispersion resin, a sequestering agent and a pigment;
  • the sequestering agent contains one or more selected from the group consisting of amine-modified epoxy resins having a hydroxyl value of 150 mgKOH / g or more and 650 mgKOH / g or less and an amine value of 30 mgKOH / g or more and 190 mgKOH / g or less and a polyhydric acid.
  • the above pigment dispersion paste An embodiment prepared by mixing the metal compound (B), the pigment-dispersed resin, and a sealing agent, and mixing the obtained mixture, the pigment-dispersed resin, and the pigment.
  • the pigment dispersion paste contains a metal compound (B), a pigment dispersion resin, an organic acid, a sequestering agent and a pigment;
  • the organic acid is one or more compounds selected from the group consisting of hydroxymonocarboxylic acids and sulfonic acids.
  • the sequestering agent contains one or more selected from the group consisting of amine-modified epoxy resins having a hydroxyl value of 150 mgKOH / g or more and 650 mgKOH / g or less and an amine value of 30 mgKOH / g or more and 190 mgKOH / g or less and a polyhydric acid.
  • Pigment-dispersed resin is a resin for dispersing a pigment, and is used after being dispersed in an aqueous medium.
  • a pigment dispersion resin having a cationic group such as a modified epoxy resin having at least one or more selected from a quaternary ammonium group, a tertiary sulfonium group and a primary amine group can be used.
  • aqueous solvent ion-exchanged water or water containing a small amount of alcohols is used.
  • an amine-modified epoxy resin having a hydroxyl value of 20 mgKOH / g or more and 120 mgKOH / g or less is preferably used.
  • An amine-modified epoxy resin having a hydroxyl value of 20 mgKOH / g or more and 120 mgKOH / g or less is prepared, for example, by reacting a half-block isocyanate with a hydroxyl group of an epoxy resin having a hydroxyl group to introduce a blocked isocyanate group. can do.
  • Polyepoxide is generally used as the epoxy resin. This epoxide has an average of two or more 1,2-epoxy groups in one molecule. A useful example of such a polyepoxy is the epoxy resin described above.
  • the half-blocked isocyanate used to react with the epoxy resin is prepared by partially blocking the polyisocyanate.
  • the reaction between the polyisocyanate and the blocking agent is carried out by cooling to 40 ° C. or higher and 50 ° C. or lower while dropping the blocking agent under stirring in the presence of a curing catalyst (for example, a tin-based catalyst) as required. Is preferable.
  • the above polyisocyanate is not particularly limited as long as it has two or more isocyanate groups on average in one molecule.
  • polyisocyanate that can be used in the preparation of the blocked isocyanate curing agent can be used.
  • Examples of an appropriate blocking agent for preparing the above-mentioned half-blocked isocyanate include lower aliphatic alkyl monoalcohols having 4 or more and 20 or less carbon atoms. Specific examples thereof include butyl alcohol, amyl alcohol, hexyl alcohol, 2-ethylhexyl alcohol and heptyl alcohol.
  • the reaction between the epoxy resin and the half-block isocyanate is preferably carried out at 140 ° C. for about 1 hour.
  • tertiary amine those having 1 or more and 6 or less carbon atoms can be preferably used.
  • tertiary amines include, for example, dimethylethanolamine, trimethylamine, triethylamine, dimethylbenzylamine, diethylbenzylamine, N, N-dimethylcyclohexylamine, tri-n-butylamine, diphenethylmethylamine, dimethylaniline, N- Methylmorpholine and the like can be mentioned.
  • the neutralizing acid used in combination with the above tertiary amine is not particularly limited, and specifically, it is an inorganic acid such as hydrochloric acid, nitric acid, phosphoric acid, formic acid, acetic acid, lactic acid, or an organic acid. ..
  • the neutralizing acid is more preferably one or more acids selected from the group consisting of formic acid, acetic acid and lactic acid.
  • the reaction between the neutralizing acid salt of the tertiary amine thus obtained and the epoxy resin can be carried out by a conventional method.
  • the epoxy resin is dissolved in a solvent such as ethylene glycol monobutyl ether, the obtained solution is heated to 60 ° C. or higher and 100 ° C. or lower, and a neutralizing acid salt of a tertiary amine is added dropwise thereto to increase the acid value.
  • the reaction mixture is kept at 60 ° C. or higher and 100 ° C. or lower until the value becomes 1.
  • the amine-modified epoxy resin having a hydroxyl value of 20 mgKOH / g or more and 120 mgKOH / g or less preferably has an epoxy equivalent of 1000 or more and 1800 or less.
  • the epoxy equivalent is more preferably 1200 or more and 1700 or less.
  • the amine-modified epoxy resin having a hydroxyl value of 20 mgKOH / g or more and 120 mgKOH / g or less preferably has a number average molecular weight of 1500 or more and 2700 or less.
  • the amine-modified epoxy resin having a hydroxyl value of 20 mgKOH / g or more and 120 mgKOH / g or less preferably has a quaternary ammonium group of 35 mEq (milligram equivalent) or more and 70 mEq or less per 100 g, and a quaternary ammonium group of 35 mEq or more and 55 mEq or less per 100 g. It is more preferable to have an ammonium group.
  • the amount of the quaternary ammonium group is in the above range, there is an advantage that the pigment dispersion performance is improved and the coating workability of the electrodeposition coating composition is improved.
  • pigments usually used in electrodeposition coating compositions can be used.
  • pigments for example, commonly used inorganic and organic pigments, such as colored pigments such as titanium white (titanium dioxide), carbon black and red iron oxide; such as kaolin, talc, aluminum silicate, calcium carbonate, mica and clay.
  • Constituent pigments; iron phosphate, aluminum phosphate, calcium phosphate, aluminum tripolyphosphate, and rust preventive pigments such as aluminum phosphate, aluminum zinc phosphate, and the like.
  • the pigment is preferably used in an amount of 1% by mass or more and 30% by mass or less with respect to the resin solid content of the cationic electrodeposition coating composition.
  • Organic Acid it is more preferable to use an organic acid in the preparation of the pigment dispersion paste.
  • an organic acid used in the present invention, the above metal compound (B) and the organic acid are mixed in advance to prepare a mixture.
  • the solubility and dispersibility of the metal compound (B) are improved, thereby improving the catalytic activity and forming a coating film having excellent curability and corrosion resistance. There is an advantage that it can be done.
  • the organic acid is, for example, one or more compounds selected from the group consisting of hydroxymonocarboxylic acids and sulfonic acids.
  • hydroxycarboxylic acid include the following compounds; a) Monohydroxymonocarboxylic acids such as lactic acid and glycolic acid, which have a total carbon number of 2 or more and 5 or less, preferably 2 or more and 4 or less, particularly aliphatic monohydroxymonocarboxylic acids; b) Dihydroxymonocarboxylic acids such as dimethylolpropionic acid (DMPA) and glyceric acid having a total carbon number of 3 to 7 or less, preferably 3 or more and 6 or less, particularly aliphatic dihydroxymonocarboxylic acids.
  • DMPA dimethylolpropionic acid
  • glyceric acid having a total carbon number of 3 to 7 or less, preferably 3 or more and 6 or less, particularly aliphatic dihydroxymonocarboxylic acids.
  • the sulfonic acid is an organic sulfonic acid, and examples thereof include alkane sulfonic acids having a total carbon atom number of 1 or more and 5 or less, preferably 1 or more and 3 or less, such as methane sulfonic acid and ethane sulfonic acid.
  • organic acid it is more preferable to use one or more selected from the group consisting of lactic acid, dimethylol propionic acid and methanesulfonic acid.
  • the form of use of the organic acid is not particularly limited, and examples thereof include a solid form, a liquid form, and a solution form dissolved in a solvent (particularly an aqueous solution form).
  • the organic acid is preferably used in the form of an aqueous solution.
  • the solvent that can be used for preparing an aqueous solution of an organic acid include water such as ion-exchanged water, purified water, and distilled water, and an aqueous solvent containing water as a main component.
  • the aqueous solvent may contain, if necessary, an organic solvent (for example, a water-soluble or water-miscible organic solvent such as an alcohol, an ester, or a ketone).
  • the metal element contained in the metal compound (B) in the present invention is one or more metal elements selected from the group consisting of Y, La, Ce, Nd, Pr and Bi, all of which are trivalent cations. It is an element that becomes. Then, one or more compounds selected from the group consisting of hydroxymonocarboxylic acid and sulfonic acid, which are the organic acids, are all monovalent acids.
  • the total valence of anions produced by the organic acid is less than the total valence (that is, the number of moles of the metal element ⁇ 3).
  • the pigment dispersion paste contains the metal compound (B) and the organic acid in the above molar ratio, so that the appearance of the cured electrodeposition coating film obtained is not deteriorated.
  • excellent repellency prevention performance can be obtained.
  • the details of this mechanism are not always clear and are not bound by theory, but for the total valence of cations due to metal elements (that is, the number of moles of metal elements x 3), the number of anions due to organic acids Even when the metal compound (B) and the organic acid are contained in the electrodeposition coating composition due to the state where the total valence (the number of moles of the organic acid) is not satisfied, the electrodeposition coating composition This is thought to be because the conductivity is kept within an appropriate range.
  • a sealant is used in the preparation of the pigment dispersion paste.
  • the sequestering agent comprises one or more selected from the group consisting of amine-modified epoxy resins having a hydroxyl value of 150 mgKOH / g or more and 650 mgKOH / g or less and an amine value of 30 mgKOH / g or more and 190 mgKOH / g or less. Either one of the above may be used as the sequestering agent, or may be used in combination.
  • Amine-modified epoxy resin having a hydroxyl value of 150 mgKOH / g or more and 650 mgKOH / g or less and an amine value of 30 mgKOH / g or more and 190 mgKOH / g or less reacts an amine compound with an oxylane ring in the epoxy resin skeleton. It can be prepared by denaturing.
  • the amine-modified epoxy resin can be prepared in the same manner as the amine-modified epoxy resin of the amine-modified resin described above.
  • the amine-modified epoxy resin the amine-modified epoxy resin in the amine-modified resin may be used as it is. In the present invention, the same resin may be used or different resins may be used as the amine-modified epoxy resin and the amine-modified epoxy resin of the amine-modified resin.
  • the amine to be reacted with the oxylan ring of the epoxy resin contains 50% by mass or more of secondary amine. It is preferable that the secondary amine having 95% by mass or less and the blocked primary amine is 0% by mass or more and 30% by mass or less, and the primary amine is 0% by mass or more and 20% by mass or less.
  • the sealing performance is satisfactorily exhibited and the obtained pigment dispersion paste is obtained.
  • the dispersion stability of the epoxy is improved and an electrodeposition coating composition having excellent coating stability can be obtained.
  • the amine-modified epoxy resin having a hydroxyl value of 150 mgKOH / g or more and 650 mgKOH / g or less and an amine value of 30 mgKOH / g or more and 190 mgKOH / g or less preferably has a number average molecular weight in the range of 1,000 or more and 5,000 or less.
  • the number average molecular weight of the amine-modified epoxy resin is more preferably in the range of 2,000 or more and 3,500 or less.
  • the number average molecular weight of the amine-modified epoxy resin is 1,000 or more, the physical properties such as solvent resistance and corrosion resistance of the obtained cured electrodeposition coating film are improved.
  • the number average molecular weight of the amine-modified epoxy resin is 5,000 or less, the dispersibility and dispersion stability of the obtained pigment dispersion paste are improved.
  • the amine-modified epoxy resin having a hydroxyl value of 150 mgKOH / g or more and 650 mgKOH / g or less and an amine value of 30 mgKOH / g or more and 190 mgKOH / g or less has a milligram equivalent (mEq (B)) of a base with respect to 100 g of the resin solid content of 50 to 350. Is preferable.
  • mEq (B) of the amine-modified epoxy resin is within the above range, there is an advantage that good storage stability of the pigment-dispersed paste can be ensured.
  • the milligram equivalent (mEq (B)) of the base with respect to 100 g of the solid content of the amine-modified epoxy resin can be adjusted by the type and amount of the amine compound to be reacted in the preparation of the amine-modified epoxy resin.
  • mEq (B) is an abbreviation for mgEquivalent (base), which is the milligram equivalent of a base per 100 g of solid content of the resin.
  • base the milligram equivalent of a base per 100 g of solid content of the resin.
  • About 10 g of the solid content of the electrodeposition coating composition is precisely weighed and dissolved in about 50 ml of a solvent (THF: tetrahydrofuran), and then 7.5 ml of anhydrous acetic acid and 2.5 ml of acetic acid are added to obtain an automatic potentiometric titration.
  • solvent tetrahydrofuran
  • the base content in the amine-modified epoxy resin is quantified and measured by performing potentiometric titration with a 0.1N acetic acid perchlorate solution using a titrator (for example, manufactured by Kyoto Denshi Kogyo Co., Ltd., APB-410, etc.). be able to.
  • a titrator for example, manufactured by Kyoto Denshi Kogyo Co., Ltd., APB-410, etc.
  • an amine-modified epoxy resin having a hydroxyl value of 150 mgKOH / g or more and 650 mgKOH / g or less and an amine value of 30 mgKOH / g or more and 190 mgKOH / g or less is used, it is preferably prepared and used in the state of a resin emulsion. ..
  • One aspect of the method for preparing the resin emulsion is a method for preparing the resin emulsion in the same manner as the resin emulsion that can be used as the coating film-forming resin (A).
  • each of the amine-modified epoxy resin and the blocked isocyanate curing agent is dissolved in an organic solvent to prepare a solution, and these solutions are mixed and then dispersed in water using a neutralizing acid.
  • the amine-modified epoxy resin may be dissolved in an organic solvent to prepare a solution, which may be dispersed in water using a neutralizing acid.
  • Examples of the neutralizing acid that can be used in the preparation of the resin emulsion include organic acids such as methanesulfonic acid, sulfamic acid, lactic acid, dimethylolpropionic acid, formic acid and acetic acid.
  • organic acids such as methanesulfonic acid, sulfamic acid, lactic acid, dimethylolpropionic acid, formic acid and acetic acid.
  • the neutralizing acid it is more preferable to use one or more acids selected from the group consisting of formic acid, acetic acid and lactic acid.
  • the amount of the amine-modified epoxy resin contained in the pigment-dispersed paste is the amount of the amine-modified epoxy resin solid content relative to 100 parts by mass of the resin solid content of the pigment-dispersed resin. It is preferably 0.02 parts by mass or more and 3 parts by mass or less, more preferably 0.03 parts by mass or more and 1 part by mass or less, and 0.06 parts by mass or more and 0.4 parts by mass or less. More preferred.
  • the amount of the amine-modified epoxy resin is within the above range, there is an advantage that the effect as a sealing agent and the curability can be ensured.
  • polyvalent acid refers to a compound having two or more monovalent acid groups or a compound having a divalent or higher acid group.
  • the polyhydric acid is preferably one or more selected from the group consisting of compounds having two or more carboxylic acid groups and compounds having phosphoric acid groups.
  • polyhydric acid for example, Compounds with 2 or more carboxylic acid groups and 2 to 6 carbon atoms, such as tartaric acid, grape acid, citric acid, malic acid, hydroxymalonic acid, malonic acid, succinic acid, glutanic acid, adipic acid, etc .; Polymers with two or more carboxylic acid groups, such as polyacrylic acid; Examples of compounds having a phosphoric acid group include phosphoric acid and condensed phosphoric acid (for example, diphosphoric acid, triphosphoric acid, polyphosphoric acid, cyclophosphoric acid, etc.).
  • condensed phosphoric acid means an inorganic compound having two or more phosphoric acid groups.
  • Condensed phosphoric acid can be prepared, for example, by a dehydration reaction of orthophosphoric acid (H 3 PO 4 ) or a similar reaction.
  • the polyvalent acid is preferably one or more selected from the group consisting of tartaric acid, citric acid, phosphoric acid, condensed phosphoric acid, malic acid and polyacrylic acid, and is preferably a group consisting of tartaric acid, citric acid and malic acid. It is more preferable that one or more selected from the above.
  • the amount of polyhydric acid contained in the pigment-dispersed paste is preferably 0.01 parts by mass or more and 10 parts by mass or less, and 0.08 parts by mass or more and 5 by mass or less, based on 100 parts by mass of the resin solid content of the pigment-dispersed resin. It is more preferably less than parts by mass, and even more preferably 0.09 parts by mass or more and 3.5 parts by mass or less.
  • a sequestering agent containing the above is used.
  • the pigment dispersion paste is prepared by mixing the mixture obtained by mixing the metal compound (B) and the organic acid, the pigment dispersion resin, the sealing agent, and then the pigment. Will be done. As a result, the dispersion stability of the obtained pigment dispersion paste is improved, and an electrodeposition coating composition having excellent coating stability can be obtained.
  • the metal compound (B) is in a finely dispersed state by mixing the metal compound (B) and the organic acid in advance. Specifically, it is considered that some metal compounds (B) are dissolved in the organic acid, and some other metal compounds (B) are dispersed together with the organic acid (for example, chelate-like dispersion).
  • the organic acid for example, chelate-like dispersion.
  • the coating state of the metal compound (B) at this stage is not sufficient. Therefore, when a pigment is added, the pigment and the metal compound (B) may react with each other and the coating state may be disrupted. Therefore, it is considered that by using a sealing agent together with the pigment-dispersed resin, the pigment-dispersed resin is self-aggregated and the coating of the metal compound (B) with the loose pigment-dispersed resin becomes strong. Since this self-cohesive force is strong, there is an advantage that good dispersion stability can be obtained even if the amount of the pigment-dispersed resin is reduced by using the sealing agent together with the pigment-dispersed resin. That is, in the present specification, the sequestering agent means a component having an action of strengthening the coating performance of the pigment-dispersed resin that coats at least a part of the metal compound (B).
  • the pigment dispersion paste is prepared by a step of mixing a mixture obtained by mixing the metal compound (B) and the pigment dispersion resin, the pigment dispersion resin, and the pigment. To.
  • the metal compound (B) and the pigment dispersion resin that is, a part of the pigment dispersion resin contained in the electrodeposition coating composition
  • the pigment dispersion resin (that is, the rest of the pigment dispersion resin contained in the electrodeposition coating composition) and the pigment are mixed with the obtained mixture.
  • Mixing conditions such as temperature and stirring speed in mixing the metal compound (B) and the pigment-dispersed resin may be conditions usually performed in the production of a coating composition, for example, 10 ° C. or higher and 50 ° C. or lower, preferably 20 ° C. or higher.
  • the stirring speed can be such that a stirring flow capable of dispersing each component is generated at ° C. or higher and 40 ° C. or lower.
  • the stirring time can be arbitrarily selected depending on the scale of the reaction system, the stirring device, and the like.
  • the stirring time may be, for example, 5 minutes or more and 2 hours or less.
  • the mixture thus obtained is mixed with the pigment dispersion resin and the pigment.
  • the method for mixing the pigment-dispersed resin and the pigment may be any method.
  • the remaining pigment dispersion resin and pigment may be mixed in advance and then mixed with the mixture obtained from the above.
  • This mixing prepares a pigment-dispersed paste.
  • the conditions such as the temperature and the stirring speed in this mixing may be the conditions usually performed in the production of the coating composition, for example, the pigment is dispersed at 10 ° C. or higher and 50 ° C. or lower, preferably 20 ° C. or higher and 40 ° C. or lower.
  • the stirring speed can be such that a stirring flow is generated.
  • the stirring time is preferably, for example, until the dispersed particle size of the pigment is 10 ⁇ m or less.
  • the dispersed particle size of the pigment can be confirmed by measuring the volume average particle size of the pigment.
  • the pigment dispersion paste is a mixture obtained by mixing the metal compound (B), the pigment dispersion resin, and a sealing agent, and the pigment dispersion resin and the pigment are mixed. Prepared by the process.
  • the metal compound (B), the pigment dispersion resin (that is, a part of the pigment dispersion resin contained in the electrodeposition coating composition), and the sealing agent are mixed.
  • the sequestering agent is preferably added after mixing the metal compound (B) and the pigment-dispersed resin.
  • the pigment-dispersed resin (that is, the rest of the pigment-dispersed resin contained in the electrodeposition coating composition) and the pigment are mixed with the obtained mixture.
  • the method for mixing the pigment-dispersed resin and the pigment with respect to the obtained mixture may be any method.
  • the remaining pigment dispersion resin and pigment may be mixed in advance and then mixed with the mixture obtained from the above.
  • the mixing conditions such as the mixing temperature and the stirring speed in this embodiment may be the conditions normally performed in the production of the coating composition, and more specifically, the same conditions as those in the above-mentioned Example 1.
  • the pigment dispersion paste is prepared by first mixing the metal compound (B) and the organic acid in advance, and then the obtained mixture, the metal compound (B), and the pigment dispersion resin. It is prepared by a step of mixing the mixture obtained by mixing the sequestering agent, the pigment dispersion resin, and the pigment.
  • the metal compound (B) and the organic acid are mixed prior to other components to prepare a mixture.
  • the solubility and dispersibility of the metal compound (B) are improved.
  • the catalytic activity is improved, and a coating film having excellent curability and corrosion resistance can be formed.
  • the particles of the metal compound (B) are dispersed by stirring in an organic acid aqueous solution obtained by mixing the organic acid and a solvent (particularly an aqueous solvent). It can be done by letting.
  • the conditions such as the temperature and the stirring speed in the mixing may be the conditions usually performed in the production of the coating composition, for example, at a stirring speed of 10 ° C. or higher and 30 ° C. or lower, preferably at room temperature, so that a stirring flow is generated. It can be carried out.
  • the stirring time can be appropriately selected according to the size of the reaction system, and can be selected, for example, in the range of 0.1 hours or more and 24 hours or less.
  • the mixture thus obtained, the pigment dispersion resin, and the sequestering agent are mixed to prepare a dispersion.
  • the mixing order of the mixture, the pigment dispersion resin and the sealing agent may be arbitrary.
  • the above mixture, pigment dispersion resin and sequestering agent may be added and mixed at the same time, the sequestering agent may be added after mixing the mixture and the pigment dispersion resin, and the pigment dispersion resin may be added after the mixture and the sequestering agent are mixed. May be added.
  • Conditions such as temperature and stirring speed in this mixing may be conditions usually performed in the production of a coating composition, for example, at 10 ° C. or higher and 50 ° C. or lower, preferably 20 ° C. or higher and 40 ° C.
  • the stirring speed can be such that a stirring flow capable of dispersing the resin and the sequestering agent is generated.
  • the stirring time can be arbitrarily selected depending on the scale of the reaction system, the stirring device, and the like. The stirring time may be, for example, 5 minutes or more and 1 hour or less.
  • a pigment dispersion paste is prepared by mixing a pigment with a dispersion liquid prepared by mixing a metal compound (B), a pigment dispersion resin and a sealing agent.
  • the conditions such as the temperature and the stirring speed in this mixing may be the conditions usually performed in the production of the coating composition, for example, the pigment is dispersed at 10 ° C. or higher and 50 ° C. or lower, preferably 20 ° C. or higher and 40 ° C. or lower.
  • the stirring speed can be such that a stirring flow is generated.
  • the stirring time is preferably, for example, until the dispersed particle size of the pigment is 10 ⁇ m or less.
  • the dispersed particle size of the pigment can be confirmed by measuring the volume average particle size of the pigment.
  • the cationic electrodeposition coating composition can be prepared by mixing the coating film forming resin (A) and the pigment dispersion paste.
  • the solid content of the cationic electrodeposition coating composition is preferably 1% by mass or more and 30% by mass or less with respect to the total amount of the electrodeposition coating composition.
  • the pH of the cationic electrodeposition coating composition is preferably 4.5 or more and 7 or less.
  • the pH of the electrodeposition coating composition can be set in the above range by adjusting the amount of neutralizing acid used, the amount of free acid added, and the like.
  • the pH of the electrodeposition coating composition can be measured using a commercially available pH meter having a temperature compensation function.
  • the milligram equivalent (mEq (A)) of the acid with respect to 100 g of the solid content of the electrodeposition coating composition is preferably 40 or more and 120 or less.
  • the milligram equivalent of acid (mEq (A)) with respect to 100 g of the resin solid content of the electrodeposition coating composition can be adjusted by the amount of neutralized acid and the amount of free acid.
  • mEq (A) is an abbreviation for mgEquivalent (acid), which is the total of milligram equivalents of all acids per 100 g of solid content of paint.
  • This mEq (A) is obtained by precisely weighing about 10 g of the solid content of the electrodeposition coating composition, dissolving it in about 50 ml of a solvent (THF: tetrahydrofuran), and then performing potentiometric titration using a 1 / 10N NaOH solution. , The amount of acid contained in the electrodeposition coating composition can be quantified and measured.
  • the cationic electrodeposition coating composition is an additive generally used in the coating field, for example, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monoethylhexyl ether, propylene glycol monobutyl ether, dipropylene glycol mono.
  • Organic solvents such as butyl ether and propylene glycol monophenyl ether, surfactants such as anti-drying agents and antifoaming agents, viscosity modifiers such as acrylic resin fine particles, repellent inhibitors, vanadium salts, copper, iron, manganese, magnesium and calcium. If necessary, an inorganic rust preventive such as salt may be contained.
  • auxiliary complexing agents may be blended depending on the purpose.
  • These additives may be mixed at the time of preparing the coating film forming resin (A), may be mixed at the time of preparing the pigment dispersion paste, or may be a mixture of the coating film forming resin (A) and the pigment dispersion paste. It may be mixed at times or after mixing.
  • Electrodeposition coating and electrodeposition coating film formation can be performed on an object to be coated.
  • electrodeposition coating using a cationic electrodeposition coating composition an object to be coated is used as a cathode, and a voltage is applied between the cathode and the anode. As a result, the electrodeposition coating film is deposited on the object to be coated.
  • electrodeposition coating is performed by immersing the object to be coated in the electrodeposition coating composition and then applying a voltage of 50 V or more and 450 V or less.
  • the bath liquid temperature of the coating composition is usually adjusted to 10 ° C. or higher and 45 ° C. or lower.
  • the time for applying the voltage varies depending on the electrodeposition conditions, but can generally be 2 minutes or more and 5 minutes or less.
  • the film thickness of the electrodeposition coating film is such that the film thickness of the electrodeposition coating film finally obtained by heat curing is preferably 5 ⁇ m or more and 40 ⁇ m or less, and more preferably 10 ⁇ m or more and 25 ⁇ m or less.
  • the electrodeposited coating film obtained as described above is 120 ° C. or higher and 260 ° C. or lower, preferably 140 ° C. or higher and 220 ° C. or lower, and 10 minutes or longer and 30 minutes or shorter after the electrodeposition process is completed. By heating, a heat-cured electrodeposition coating film is formed.
  • objects to be coated that can be energized can be used.
  • objects to be coated include cold-rolled steel sheets, hot-rolled steel sheets, stainless steel, electrogalvanized steel sheets, hot-dip galvanized steel sheets, zinc-aluminum alloy-based plated steel sheets, zinc-iron alloy-based plated steel sheets, and zinc-magnesium alloy-based plating.
  • the cationic electrodeposition coating composition has an advantage of exhibiting good anti-repellency by containing both the metal compound (B) and the silicone compound (C) within a specific content range.
  • the cationic electrodeposition coating composition also has an advantage that the appearance of the obtained cured electrodeposition coating film is also good.
  • IPDI isophorone diisocyanate 222.0 in a reaction vessel equipped with a stirrer, a cooling tube, a nitrogen introduction tube and a thermometer. Parts were added and diluted with 39.1 parts of methyl isobutyl ketone (MIBK), and then 0.2 parts of hedibutyltin dilaurate was added here.
  • MIBK methyl isobutyl ketone
  • pigment dispersion resin 710.0 parts of bisphenol A type epoxy resin (trade name: DER-331J, manufactured by Dow Chemical Co., Ltd.) and 289.6 parts of bisphenol A are charged in a reaction vessel, and 1 at 150 to 160 ° C. under a nitrogen atmosphere. Reacted for time. Then, after cooling to 120 ° C., 498.8 parts of the previously prepared 2-ethylhexanol half-blocked IPDI (MIBK solution) was added. The reaction mixture was stirred at 110-120 ° C. for 1 hour and 463.4 parts of ethylene glycol mono-n-butyl ether was added. The mixture was cooled to 85-95 ° C.
  • aminized resin (amine-modified epoxy resin). ..
  • the number average molecular weight of this resin is 2,560, the amine value (milligram equivalent of base to 100 g of resin solid content: mEq (B)) is 50 mgKOH / g (of which the amine value derived from primary amine is 14 mgKOH / g), and the hydroxyl group.
  • the valence was 240 mgKOH / g.
  • Production Example 3-2 Production of Block Isocyanate Hardener (2) 1340 parts of 4,4'-diphenylmethane diisocyanate and 277 parts of MIBK were charged into a reaction vessel and heated to 80 ° C. Then, 226 parts of ⁇ -caprolactam dissolved in 944 parts of butyl cellosolve was added dropwise at 80 ° C. over 2 hours. After further heating at 100 ° C. for 4 hours, it was confirmed by measurement of the IR spectrum that the absorption based on the isocyanate group had disappeared, and the mixture was allowed to cool. Then, 349 parts of MIBK was added to obtain a blocked isocyanate curing agent (2) (solid content 80%). The isocyanate base value was 251 mgKOH / g.
  • Production Example 4 Production of Amine-Modified Epoxy Resin Emulsion (1) 350 parts (solid content) of the amine-modified resin obtained in Production Example 2 and 75 parts (solid content) of the blocked isocyanate curing agent (1) obtained in Production Example 3-1. Minutes) and 75 parts (solid content) of the blocked isocyanate curing agent (2) obtained in Production Example 3-2 were mixed to add ethylene glycol mono-2-ethylhexyl ether to 3% (15 parts) of the solid content. It was added so as to become. Next, formic acid was added so that the amount of formic acid added was equivalent to a resin neutralization rate of 40% for neutralization. Then, ion-exchanged water was added to slowly dilute. Then, methyl isobutyl ketone was removed under reduced pressure so that the solid content became 40% to obtain an amine-modified epoxy resin emulsion (1).
  • Example 1 Production of pigment-dispersed paste 0.04 parts of 50% lactic acid aqueous solution and 0.05 parts of yttrium oxide were added to 125.7 parts of ion-exchanged water so that the solid content concentration of the dispersed paste was 47% by mass, and 1 at room temperature. Stir for hours and mix. To this, 81.4 parts (resin solid content equivalent amount) of the pigment-dispersed resin obtained in Production Example 1 was added, and the mixture was stirred at room temperature for 1 hour at 1000 rpm.
  • Example 2 Production of pigment-dispersed paste 0.04 parts of 50% lactic acid aqueous solution and 0.05 parts of lanthanum oxide were added to 125.7 parts of ion-exchanged water so that the solid content concentration of the dispersed paste was 47% by mass, and 1 at room temperature. Stir for hours and mix. To this, 81.4 parts (resin solid content equivalent amount) of the pigment-dispersed resin obtained in Production Example 1 was added, and the mixture was stirred at room temperature for 1 hour at 1000 rpm.
  • Example 3 Production of pigment-dispersed paste 0.04 parts of 50% lactic acid aqueous solution and 0.05 parts of cerium oxide were added to 125.7 parts of ion-exchanged water so that the solid content concentration of the dispersed paste was 47% by mass, and 1 at room temperature. Stir for hours and mix. To this, 81.4 parts (resin solid content equivalent amount) of the pigment-dispersed resin obtained in Production Example 1 was added, and the mixture was stirred at room temperature for 1 hour at 1000 rpm.
  • Example 4 Production of pigment-dispersed paste 0.04 parts of 50% lactic acid aqueous solution and 0.05 parts of neodymium oxide were added to 125.7 parts of ion-exchanged water so that the solid content concentration of the dispersed paste was 47% by mass, and 1 at room temperature. Stir for hours and mix. To this, 81.4 parts (resin solid content equivalent amount) of the pigment-dispersed resin obtained in Production Example 1 was added, and the mixture was stirred at room temperature for 1 hour at 1000 rpm.
  • Example 5 Production of pigment-dispersed paste 0.04 parts of 50% lactic acid aqueous solution and 0.05 parts of bismuth oxide were added to 125.7 parts of ion-exchanged water so that the solid content concentration of the dispersed paste was 47% by mass, and 1 at room temperature. Stir for hours and mix. To this, 81.4 parts (resin solid content equivalent amount) of the pigment-dispersed resin obtained in Production Example 1 was added, and the mixture was stirred at room temperature for 1 hour at 1000 rpm.
  • Example 6 Production of Pigment Dispersion Paste To make the solid content concentration of the dispersion paste 47% by mass, 0.006 part of a 50% lactic acid aqueous solution and 0.01 part of bismuth oxide were added to 130.4 parts of ion-exchanged water, and 1 part at room temperature. Stirred for hours. Further, 0.037 parts of a 50% aqueous lactic acid solution and 0.04 parts of lanthanum oxide were added thereto, and the mixture was stirred and mixed at room temperature for 1 hour. To this, 85.2 parts (resin solid content equivalent amount) of the pigment-dispersed resin obtained in Production Example 1 was added, and the mixture was stirred at room temperature for 1 hour at 1000 rpm.
  • Example 7 A cationic electrodeposition coating composition was produced in the same manner as in Example 1 except that the amount of the silicone compound was changed to 7.4 parts in the production of the electrodeposition coating composition.
  • Example 8 A cationic electrodeposition coating composition was produced in the same manner as in Example 2 except that the amount of the silicone compound was changed to 7.4 parts in the production of the electrodeposition coating composition.
  • Example 9 A cationic electrodeposition coating composition was produced in the same manner as in Example 3 except that the amount of the silicone compound was changed to 7.4 parts in the production of the electrodeposition coating composition.
  • Example 10 A cationic electrodeposition coating composition was produced in the same manner as in Example 4 except that the amount of the silicone compound was changed to 7.4 parts in the production of the electrodeposition coating composition.
  • Example 11 A cationic electrodeposition coating composition was produced in the same manner as in Example 5 except that the amount of the silicone compound was changed to 7.4 parts in the production of the electrodeposition coating composition.
  • Example 12 A cationic electrodeposition coating composition was produced in the same manner as in Example 6 except that the amount of the silicone compound was changed to 7.4 parts in the production of the electrodeposition coating composition.
  • Example 13 Examples except that 0.78 parts of a 50% lactic acid aqueous solution and 1 part of yttrium oxide were used in the production of the pigment dispersion paste, and 2.4 parts of the silicone compound was used in the production of the electrodeposition coating composition.
  • a cationic electrodeposition coating composition was produced in the same manner as in 1.
  • Example 14 Examples except that 0.73 parts of a 50% lactic acid aqueous solution and 1 part of yttrium oxide were used in the production of the pigment dispersion paste, and 2.4 parts of the silicone compound was used in the production of the electrodeposition coating composition.
  • a cationic electrodeposition coating composition was produced in the same manner as in 2.
  • Example 15 Examples except that 0.70 parts of a 50% lactic acid aqueous solution and 1 part of yttrium oxide were used in the production of the pigment dispersion paste, and 2.4 parts of the silicone compound was used in the production of the electrodeposition coating composition.
  • a cationic electrodeposition coating composition was produced in the same manner as in 3.
  • Example 16 Examples except that 0.74 parts of a 50% lactic acid aqueous solution and 1 part of yttrium oxide were used in the production of the pigment dispersion paste, and 2.4 parts of the silicone compound was used in the production of the electrodeposition coating composition.
  • a cationic electrodeposition coating composition was produced in the same manner as in 4.
  • Example 17 Examples except that 0.77 parts of a 50% lactic acid aqueous solution and 1 part of yttrium oxide were used in the production of the pigment dispersion paste, and 2.4 parts of the silicone compound was used in the production of the electrodeposition coating composition.
  • a cationic electrodeposition coating composition was produced in the same manner as in 5.
  • Example 18 Production of pigment-dispersed paste 0.15 parts of 50% lactic acid aqueous solution and 0.2 parts of bismuth oxide were added to 130.1 parts of ion-exchanged water so that the solid content concentration of the dispersed paste was 47% by mass, and 1 at room temperature. Stirred for hours. Further, 0.88 parts of a 50% aqueous lactic acid solution and 0.8 parts of lanthanum oxide were added thereto, and the mixture was stirred and mixed at room temperature for 1 hour. To this, 85.2 parts (resin solid content equivalent amount) of the pigment-dispersed resin obtained in Production Example 1 was added, and the mixture was stirred at room temperature for 1 hour at 1000 rpm.
  • Example 19 A cationic electrodeposition coating composition was produced in the same manner as in Example 1 except that 2.34 parts of a 50% lactic acid aqueous solution and 3 parts of yttrium oxide were used in the production of the pigment dispersion paste.
  • Example 20 A cationic electrodeposition coating composition was produced in the same manner as in Example 2 except that 2.2 parts of a 50% lactic acid aqueous solution and 3 parts of lanthanum oxide were used in the production of the pigment dispersion paste.
  • Example 21 A cationic electrodeposition coating composition was produced in the same manner as in Example 3 except that 2.1 parts of a 50% lactic acid aqueous solution and 3 parts of cerium oxide were used in the production of the pigment dispersion paste.
  • Example 22 A cationic electrodeposition coating composition was produced in the same manner as in Example 4 except that 2.2 parts of a 50% lactic acid aqueous solution and 3 parts of neodymium oxide were used in the production of the pigment dispersion paste.
  • Example 23 A cationic electrodeposition coating composition was produced in the same manner as in Example 5 except that 2.3 parts of a 50% lactic acid aqueous solution and 3 parts of bismuth oxide were used in the production of the pigment dispersion paste.
  • Example 24 Production of Pigment Dispersion Paste Add 0.43 parts of 50% lactic acid aqueous solution and 0.6 parts of bismuth oxide to 128.1 parts of ion-exchanged water so that the solid content concentration of the dispersion paste becomes 47% by mass, and 1 at room temperature. Stirred for hours. To this, 2.6 parts of a 50% aqueous lactic acid solution and 2.4 parts of lanthanum oxide were further added, and the mixture was stirred and mixed at room temperature for 1 hour. To this, 85.2 parts (resin solid content equivalent amount) of the pigment-dispersed resin obtained in Production Example 1 was added, and the mixture was stirred at room temperature for 13 hours at 1000 rpm.
  • Example 25 A cationic electrodeposition coating composition was produced in the same manner as in Example 19 except that the amount of the silicone compound was changed to 7.4 parts in the production of the electrodeposition coating composition.
  • Example 26 A cationic electrodeposition coating composition was produced in the same manner as in Example 20 except that the amount of the silicone compound was changed to 7.4 parts in the production of the electrodeposition coating composition.
  • Example 27 A cationic electrodeposition coating composition was produced in the same manner as in Example 21 except that the amount of the silicone compound was changed to 7.4 parts in the production of the electrodeposition coating composition.
  • Example 28 A cationic electrodeposition coating composition was produced in the same manner as in Example 22 except that the amount of the silicone compound was changed to 7.4 parts in the production of the electrodeposition coating composition.
  • Example 29 A cationic electrodeposition coating composition was produced in the same manner as in Example 23, except that the amount of the silicone compound was changed to 7.4 parts in the production of the electrodeposition coating composition.
  • Example 30 A cationic electrodeposition coating composition was produced in the same manner as in Example 24, except that the amount of the silicone compound was changed to 7.4 parts in the production of the electrodeposition coating composition.
  • Comparative Example 1 Except for the fact that 0.019 parts of a 50% lactic acid aqueous solution and 0.025 parts of yttrium oxide were used in the production of the pigment dispersion paste, and 0.008 parts of the silicone compound was used in the production of the electrodeposition coating composition.
  • a cationic electrodeposition coating composition was produced in the same manner as in Example 1.
  • Comparative Example 2 Except for the fact that 0.018 parts of a 50% lactic acid aqueous solution and 0.025 parts of lanthanum oxide were used in the production of the pigment dispersion paste, and 0.008 parts of the silicone compound was used in the production of the electrodeposition coating composition.
  • a cationic electrodeposition coating composition was produced in the same manner as in Example 2.
  • Comparative Example 3 Except for the fact that 0.018 parts of a 50% lactic acid aqueous solution and 0.025 parts of cerium oxide were used in the production of the pigment dispersion paste, and 0.008 parts of the silicone compound was used in the production of the electrodeposition coating composition.
  • a cationic electrodeposition coating composition was produced in the same manner as in Example 3.
  • Comparative Example 4 Except for the fact that 0.018 parts of a 50% lactic acid aqueous solution and 0.025 parts of neodymium oxide were used in the production of the pigment dispersion paste, and 0.008 parts of the silicone compound was used in the production of the electrodeposition coating composition.
  • a cationic electrodeposition coating composition was produced in the same manner as in Example 4.
  • Comparative Example 5 Except for the fact that 0.019 parts of a 50% lactic acid aqueous solution and 0.025 parts of bismuth oxide were used in the production of the pigment dispersion paste, and 0.008 parts of the silicone compound was used in the production of the electrodeposition coating composition.
  • a cationic electrodeposition coating composition was produced in the same manner as in Example 5.
  • Comparative Example 6 Production of Pigment Dispersion Paste Add 0.004 part of 50% lactic acid aqueous solution and 0.005 part of bismuth oxide to 131.1 parts of ion-exchanged water so that the solid content concentration of the dispersion paste becomes 47% by mass, and 1 at room temperature. Stirred for hours. Further, 0.021 parts of a 50% aqueous lactic acid solution and 0.02 parts of lanthanum oxide were added thereto, and the mixture was stirred and mixed at room temperature for 1 hour. To this, 85.2 parts (resin solid content equivalent amount) of the pigment-dispersed resin obtained in Production Example 1 was added, and the mixture was stirred at room temperature for 1 hour at 1000 rpm.
  • Comparative Example 7 A cationic electrodeposition coating composition was produced in the same manner as in Comparative Example 1 except that the amount of the silicone compound was changed to 9.72 parts in the production of the electrodeposition coating composition.
  • Comparative Example 8 A cationic electrodeposition coating composition was produced in the same manner as in Comparative Example 2 except that the amount of the silicone compound was changed to 9.72 parts in the production of the electrodeposition coating composition.
  • Comparative Example 9 A cationic electrodeposition coating composition was produced in the same manner as in Comparative Example 3 except that the amount of the silicone compound was changed to 9.72 parts in the production of the electrodeposition coating composition.
  • Comparative Example 10 A cationic electrodeposition coating composition was produced in the same manner as in Comparative Example 4 except that the amount of the silicone compound was changed to 9.72 parts in the production of the electrodeposition coating composition.
  • Comparative Example 11 A cationic electrodeposition coating composition was produced in the same manner as in Comparative Example 5, except that the amount of the silicone compound was changed to 9.72 parts in the production of the electrodeposition coating composition.
  • Comparative Example 12 A cationic electrodeposition coating composition was produced in the same manner as in Comparative Example 6 except that the amount of the silicone compound was changed to 9.72 parts in the production of the electrodeposition coating composition.
  • a cationic electrodeposition coating composition was produced in the same manner as in 1.
  • Comparative Example 14 Examples except that 2.94 parts of a 50% lactic acid aqueous solution and 4 parts of lanthanum oxide were used in the production of the pigment dispersion paste, and 0.008 parts of the silicone compound was used in the production of the electrodeposition coating composition.
  • a cationic electrodeposition coating composition was produced in the same manner as in 2.
  • Comparative Example 15 Examples except that 2.10 parts of a 50% lactic acid aqueous solution and 4 parts of cerium oxide were used in the production of the pigment dispersion paste, and 0.008 parts of the silicone compound was used in the production of the electrodeposition coating composition.
  • a cationic electrodeposition coating composition was produced in the same manner as in 3.
  • Comparative Example 16 Examples except that 2.95 parts of a 50% lactic acid aqueous solution and 4 parts of neodymium oxide were used in the production of the pigment dispersion paste, and 0.008 parts of the silicone compound was used in the production of the electrodeposition coating composition.
  • a cationic electrodeposition coating composition was produced in the same manner as in 4.
  • Comparative Example 17 Examples except that 3.09 parts of a 50% lactic acid aqueous solution and 4 parts of bismuth oxide were used in the production of the pigment dispersion paste, and 0.008 parts of the silicone compound was used in the production of the electrodeposition coating composition.
  • a cationic electrodeposition coating composition was produced in the same manner as in 5.
  • Comparative Example 18 Production of Pigment Dispersion Paste Add 0.58 parts of 50% lactic acid aqueous solution and 0.75 parts of bismuth oxide to 127.1 parts of ion-exchanged water so that the solid content concentration of the dispersion paste becomes 47% by mass, and 1 at room temperature. Stirred for hours. To this, 3.49 parts of a 50% aqueous lactic acid solution and 3.25 parts of lanthanum oxide were further added, and the mixture was stirred and mixed at room temperature for 1 hour. To this, 85.2 parts (resin solid content equivalent amount) of the pigment-dispersed resin obtained in Production Example 1 was added, and the mixture was stirred at room temperature for 1 hour at 1000 rpm.
  • Comparative Example 19 A cationic electrodeposition coating composition was produced in the same manner as in Comparative Example 13 except that the amount of the silicone compound was changed to 9.72 parts in the production of the electrodeposition coating composition.
  • Comparative Example 20 A cationic electrodeposition coating composition was produced in the same manner as in Comparative Example 14, except that the amount of the silicone compound was changed to 9.72 parts in the production of the electrodeposition coating composition.
  • Comparative Example 21 A cationic electrodeposition coating composition was produced in the same manner as in Comparative Example 15 except that the amount of the silicone compound was changed to 9.72 parts in the production of the electrodeposition coating composition.
  • Comparative Example 22 A cationic electrodeposition coating composition was produced in the same manner as in Comparative Example 16 except that the amount of the silicone compound was changed to 9.72 parts in the production of the electrodeposition coating composition.
  • Comparative Example 23 A cationic electrodeposition coating composition was produced in the same manner as in Comparative Example 17, except that the amount of the silicone compound was changed to 9.72 parts in the production of the electrodeposition coating composition.
  • Comparative Example 24 A cationic electrodeposition coating composition was produced in the same manner as in Comparative Example 18 except that the amount of the silicone compound was changed to 9.72 parts in the production of the electrodeposition coating composition.
  • Comparative Example 25 Production of pigment-dispersed paste 0.6 parts of 50% lactic acid aqueous solution and 1 part of potassium hydroxide were added to 125.2 parts of ion-exchanged water so that the solid content concentration of the dispersed paste was 47% by mass, and the mixture was added at room temperature for 1 hour. Stirred and mixed. To this, 81.4 parts (resin solid content equivalent amount) of the pigment-dispersed resin obtained in Production Example 1 was added, and the mixture was stirred at room temperature for 1 hour at 1000 rpm.
  • Comparative Example 26 Production of Pigment Dispersion Paste Add 0.6 parts of 50% lactic acid aqueous solution and 1 part of calcium oxide to 125.2 parts of ion-exchanged water so that the solid content concentration of the dispersion paste becomes 47% by mass, and stir at room temperature for 1 hour. And mixed. To this, 81.4 parts (resin solid content equivalent amount) of the pigment-dispersed resin obtained in Production Example 1 was added, and the mixture was stirred at room temperature for 1 hour at 1000 rpm.
  • Electroplated Coating Composition A cationic electrodeposition coating composition was produced using the pigment dispersion paste obtained above by the same procedure as in Comparative Example 25.
  • SP 11.5, solid content 52%) composed of methyl methacrylate, n-butyl acrylate, and hydroxyethyl methacrylate as an anti-repellent agent.
  • a cationic electrodeposition coating composition was produced in the same manner as in Example 18 except that it was used.
  • a cold-rolled steel sheet (JIS G3141, SPCC-SD) was immersed in a surf cleaner EC90 (manufactured by Nippon Paint Surf Chemicals) at 50 ° C. for 2 minutes for degreasing.
  • Surf Fine GL1 manufactured by Nippon Paint Surf Chemicals
  • Surfdyne EC3200 manufactured by Nippon Paint Surf Chemicals, a zirconium chemical conversion treatment agent
  • a required amount of 2-ethylhexyl glycol was added to the cationic electrodeposition coating composition obtained above so that the film thickness of the electrodeposition coating film after curing was 20 ⁇ m. Then, after all the steel plates were embedded in the electrodeposition coating composition, the application of voltage was started immediately. An uncured electrodeposition coating film was deposited on the object to be coated (cold-rolled steel sheet) by applying a voltage under the condition that the voltage was increased for 30 seconds and held for 150 seconds after reaching 180 V. The obtained uncured electrodeposition coating film was heat-cured at 160 ° C. for 15 minutes to obtain an electrodeposition coating plate having a cured electrodeposition coating film having a film thickness of 20 ⁇ m.
  • repellency prevention (flowing oil repellency) A 10% -butyl cellosolve solution was prepared as the oil content. The above solution was added to ion-exchanged water to prepare an oil-containing aqueous solution containing 300 ppm of oil. Using the cationic electrodeposition coating compositions of the above Examples and Comparative Examples, electrodeposition coating was performed under the same voltage application conditions as above, and an uncured electrodeposition coating film was precipitated on the steel sheet. Next, a steel sheet having an uncured electrodeposition coating film was immersed in ion-exchanged water. A steel sheet having an uncured electrodeposition coating film was placed on an evaluation table having an inclination of 30 ° and allowed to stand for 3 minutes.
  • Number of repellents is 5 or less ⁇ Number of repellents is 6 or more and 15 or less ⁇ ⁇ Number of repellents is 16 or more and 30 or less and repellents are shallow and small ⁇ Number of repellents is 16 or more and 30 or less and repellents are deep and large ⁇ The number of repellents is 30 or more
  • a 10% -butyl cellosolve solution was prepared as the oil content.
  • the above solution was mixed into a 10 L electrodeposition coating composition so that the oil content was 200 ppm, and the mixture was stirred at 500 rpm for 24 hours.
  • the L-shaped steel sheet was arranged so that at least the horizontal portion (length 5 cm) of the L-shaped steel sheet obtained by bending the steel sheet into an L-shape was immersed in the electrodeposition coating composition. At this time, the L-shaped steel sheet was arranged so that the horizontal portion of the L-shaped steel sheet was horizontal to the liquid level of the electrodeposition coating composition and the vertical portion of the L-shaped steel sheet was perpendicular to the liquid level of the coating composition.
  • the dry coating film was electrodeposited to a size of 20 ⁇ m to form an uncured coating film.
  • the obtained uncured coating film was baked and cured at 160 ° C. for 15 minutes.
  • Other electrodeposition conditions are the same as the formation of the cured electrodeposition coating film prepared in the above appearance evaluation.
  • the evaluation of the repellency of the mixed oil is supposed to evaluate the repellency prevention property of the cationic electrodeposition coating composition before and during coating.
  • the surface of the coating film on the lower surface of the horizontal portion of the L-shaped steel sheet was visually observed, the number of repellents was counted, and the evaluation was performed according to the following evaluation criteria.
  • Evaluation criteria ⁇ No repellent ⁇ Number of repellents is 3 or less ⁇ ⁇ Number of repellents is 4 or more and 10 or less ⁇ Number of repellents is 11 or more and 15 or less ⁇ Number of repellents is 16 or more
  • Appearance evaluation With respect to the electrodeposition coating plate having the electrodeposition coating film obtained by the electrodeposition coating plate, the presence or absence of abnormality in the appearance of the coating film was visually evaluated.
  • the evaluation criteria are as follows. Evaluation Criteria ⁇ Has a uniform coating film appearance ⁇ ⁇ Although there are some parts that are visually recognized as uneven, it has an almost uniform coating film appearance as a whole ⁇ The coating film appearance is uneven ⁇ The appearance of the coating film is extremely uneven.
  • Comparative Examples 1 to 24 are examples in which the contents of the metal compound (B) and the silicone compound (C) are out of the above range. In these experimental examples, it was confirmed that one or both of the anti-repellency property and the appearance of the coating film were inferior.
  • Comparative Example 25 is an example in which a metal compound containing potassium (K), which is a monovalent metal element, is used.
  • Comparative Example 26 is an example in which a metal compound containing calcium (Ca), which is a divalent metal element, is used. In all of these comparative examples, it was confirmed that the repellency prevention property was inferior.
  • Comparative Example 27 is an experimental example in which an acrylic resin is used instead of the silicone compound. The SP value of the acrylic resin used in this comparative example is high, which is close to the SP value of the silicone compound used in the examples. However, in this comparative example, it was confirmed that anti-repellency could not be obtained.
  • the above cationic electrodeposition coating composition has good anti-repellency performance.
  • a cured electrodeposition coating film having a good coating film appearance can be formed.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)
PCT/JP2020/026266 2019-07-11 2020-07-03 カチオン電着塗料組成物 Ceased WO2021006220A1 (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN202080049719.8A CN114040947B (zh) 2019-07-11 2020-07-03 阳离子电沉积涂料组合物
MX2021015951A MX2021015951A (es) 2019-07-11 2020-07-03 Composición de revestimiento por electrodeposición catiónica.
EP20836845.6A EP3998316A4 (en) 2019-07-11 2020-07-03 CATHODE ELECTRODEPOSITION COATING COMPOSITION
US17/624,404 US20220332960A1 (en) 2019-07-11 2020-07-03 Cationic electrodeposition coating composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019129248A JP7401214B2 (ja) 2019-07-11 2019-07-11 カチオン電着塗料組成物
JP2019-129248 2019-07-11

Publications (1)

Publication Number Publication Date
WO2021006220A1 true WO2021006220A1 (ja) 2021-01-14

Family

ID=74114232

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/026266 Ceased WO2021006220A1 (ja) 2019-07-11 2020-07-03 カチオン電着塗料組成物

Country Status (6)

Country Link
US (1) US20220332960A1 (https=)
EP (1) EP3998316A4 (https=)
JP (1) JP7401214B2 (https=)
CN (1) CN114040947B (https=)
MX (1) MX2021015951A (https=)
WO (1) WO2021006220A1 (https=)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115197618A (zh) * 2021-04-14 2022-10-18 株式会社Kcc 丙烯酸类电沉积涂料组合物

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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 (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05306327A (ja) 1991-12-06 1993-11-19 Nippon Paint Co Ltd オキサゾリドン環含有水性樹脂および塗料
JP2009280803A (ja) * 2008-04-24 2009-12-03 Nippon Paint Co Ltd カチオン電着塗料、塗膜の形成方法及び塗膜
JP2012092293A (ja) 2010-09-29 2012-05-17 Kansai Paint Co Ltd 電着塗料用顔料分散ペースト及びカチオン電着塗料組成物
JP2017508025A (ja) * 2013-12-20 2017-03-23 ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツングＢＡＳＦ Ｃｏａｔｉｎｇｓ ＧｍｂＨ 顔料ペースト、及び水性電着材料の製造方法、それらの使用方法、電気泳動電着の方法、及びコーティングされた物品
CN106883690A (zh) * 2017-04-06 2017-06-23 广德瑞邦涂料有限公司 一种厚膜膏溶剂型电泳漆
US20180282557A1 (en) * 2017-03-31 2018-10-04 Axalta Coating Systems Ip Co., Llc Electrocoating compositon including an anti-crater agent
JP2019129248A (ja) 2018-01-25 2019-08-01 株式会社Ｓｃｒｅｅｎホールディングス 基板洗浄ブラシおよび基板洗浄装置
WO2020129817A1 (ja) * 2018-12-18 2020-06-25 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 カチオン電着塗料組成物及び硬化電着塗膜の形成方法

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6342397A (ja) * 1986-08-06 1988-02-23 Nippon Paint Co Ltd 電着塗装方法
JPS63245917A (ja) * 1987-04-01 1988-10-13 松下電器産業株式会社 固体電解コンデンサの製造方法
JPH05140489A (ja) * 1991-11-18 1993-06-08 Nippon Paint Co Ltd カチオン電着塗料組成物
DE4446440A1 (de) * 1994-12-23 1996-06-27 Hoechst Ag Wäßrige Pigmentpasten
US6033545A (en) * 1997-12-08 2000-03-07 Ppg Industries Ohio, Inc. Electrocoating processes and compositions containing polysiloxane crater control agents
JP2001192611A (ja) * 2000-01-07 2001-07-17 Nippon Paint Co Ltd カチオン電着塗料組成物
EP1798260A1 (en) * 2004-10-08 2007-06-20 Tokuyama Corporation Coating compositions and process for production thereof
US7264705B2 (en) * 2004-10-18 2007-09-04 E. I. Dupont De Nemours And Company Cathodic electrocoating compositions containing an anti-crater agent
JP5441802B2 (ja) * 2009-05-26 2014-03-12 関西ペイント株式会社 カチオン電着塗料組成物
CN102604003B (zh) * 2012-03-14 2014-07-09 大连工业大学 一种自分层有机-无机纳米复合乳液及其制备方法
CN104685012B (zh) * 2012-10-02 2016-12-14 关西涂料株式会社 阳离子电沉积涂料组合物
JP2014177514A (ja) * 2013-03-13 2014-09-25 Shinto Paint Co Ltd カチオン性電着塗料組成物
CN103319691B (zh) * 2013-06-24 2015-07-15 浩力森涂料（上海）有限公司 有机硅改性环氧电泳涂料乳液的制备方法
CN103992716B (zh) * 2014-04-16 2016-05-18 朱峰 一种用于油烟机的电泳水性特氟龙涂料及其制备方法
JP2018184489A (ja) * 2015-09-25 2018-11-22 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 カチオン電着塗料組成物の調製方法
US11466175B2 (en) * 2019-12-30 2022-10-11 Ppg Industries Ohio, Inc. Silicone-based electrodepositable coating composition

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05306327A (ja) 1991-12-06 1993-11-19 Nippon Paint Co Ltd オキサゾリドン環含有水性樹脂および塗料
JP2009280803A (ja) * 2008-04-24 2009-12-03 Nippon Paint Co Ltd カチオン電着塗料、塗膜の形成方法及び塗膜
JP2012092293A (ja) 2010-09-29 2012-05-17 Kansai Paint Co Ltd 電着塗料用顔料分散ペースト及びカチオン電着塗料組成物
JP2017508025A (ja) * 2013-12-20 2017-03-23 ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツングＢＡＳＦ Ｃｏａｔｉｎｇｓ ＧｍｂＨ 顔料ペースト、及び水性電着材料の製造方法、それらの使用方法、電気泳動電着の方法、及びコーティングされた物品
US20180282557A1 (en) * 2017-03-31 2018-10-04 Axalta Coating Systems Ip Co., Llc Electrocoating compositon including an anti-crater agent
CN106883690A (zh) * 2017-04-06 2017-06-23 广德瑞邦涂料有限公司 一种厚膜膏溶剂型电泳漆
JP2019129248A (ja) 2018-01-25 2019-08-01 株式会社Ｓｃｒｅｅｎホールディングス 基板洗浄ブラシおよび基板洗浄装置
WO2020129817A1 (ja) * 2018-12-18 2020-06-25 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 カチオン電着塗料組成物及び硬化電着塗膜の形成方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SUH, CLARKE, J.P.S.A-1, vol. 5, 1967, pages 1671 - 1681

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115197618A (zh) * 2021-04-14 2022-10-18 株式会社Kcc 丙烯酸类电沉积涂料组合物
CN115197618B (zh) * 2021-04-14 2024-02-13 株式会社Kcc 丙烯酸类电沉积涂料组合物

Also Published As

Publication number Publication date
MX2021015951A (es) 2022-04-18
JP2021014515A (ja) 2021-02-12
EP3998316A1 (en) 2022-05-18
US20220332960A1 (en) 2022-10-20
CN114040947A (zh) 2022-02-11
CN114040947B (zh) 2023-02-28
JP7401214B2 (ja) 2023-12-19
EP3998316A4 (en) 2023-07-12

Similar Documents

Publication Publication Date Title
JP6795435B2 (ja) エポキシ粘性剤およびカチオン電着塗料組成物
JP6441126B2 (ja) カチオン電着塗料組成物の調製方法
JP6871032B2 (ja) カチオン電着塗料組成物
WO2016143707A1 (ja) カチオン電着塗料組成物
WO2017051901A1 (ja) カチオン電着塗料組成物の調製方法
WO2021006220A1 (ja) カチオン電着塗料組成物
JP7064291B2 (ja) カチオン電着塗料組成物
US12480005B2 (en) Method for preparing cationic electrodeposition coating composition
JP6406848B2 (ja) 電着塗料組成物
JP6832908B2 (ja) カチオン電着塗料組成物及び硬化電着塗膜の形成方法
WO2021256193A1 (ja) カチオン電着塗料用エポキシ粘性剤の製造方法
JP2022129794A (ja) カチオン電着塗料組成物
JP6719185B2 (ja) カチオン電着塗料組成物の調製方法
JP6615552B2 (ja) カチオン電着塗料組成物
WO2025204073A1 (ja) カチオン電着塗料組成物およびその製造方法
JP2022088769A (ja) カチオン電着塗料組成物、電着塗装方法及びカチオン電着塗膜
JP2022020996A (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: 20836845

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2020836845

Country of ref document: EP

Effective date: 20220211

WWG Wipo information: grant in national office

Ref document number: 202247001694

Country of ref document: IN