WO2008050797A1 - Composition de revêtement pour électrodéposition cationique et son application - Google Patents

Composition de revêtement pour électrodéposition cationique et son application Download PDF

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Publication number
WO2008050797A1
WO2008050797A1 PCT/JP2007/070723 JP2007070723W WO2008050797A1 WO 2008050797 A1 WO2008050797 A1 WO 2008050797A1 JP 2007070723 W JP2007070723 W JP 2007070723W WO 2008050797 A1 WO2008050797 A1 WO 2008050797A1
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Prior art keywords
electrodeposition coating
parts
cationic electrodeposition
coating composition
resin particles
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PCT/JP2007/070723
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English (en)
Japanese (ja)
Inventor
Teruzo Toi
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Nippon Paint Co., Ltd.
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Priority claimed from JP2006290007A external-priority patent/JP2008106135A/ja
Priority claimed from JP2006290003A external-priority patent/JP2008106134A/ja
Application filed by Nippon Paint Co., Ltd. filed Critical Nippon Paint Co., Ltd.
Priority to AU2007310040A priority Critical patent/AU2007310040A1/en
Priority to US12/312,078 priority patent/US20100116673A1/en
Publication of WO2008050797A1 publication Critical patent/WO2008050797A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
    • C08G18/643—Reaction products of epoxy resins with at least equivalent amounts of amines
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
    • C08G18/8077—Oximes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4028—Isocyanates; Thioisocyanates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
    • C09D5/443—Polyepoxides
    • C09D5/4434—Polyepoxides characterised by the nature of the epoxy binder
    • C09D5/4438—Binder based on epoxy/amine adducts, i.e. reaction products of polyepoxides with compounds containing amino groups only
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/4488—Cathodic paints
    • C09D5/4492—Cathodic paints containing special additives, e.g. grinding agents
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/04—Electrophoretic coating characterised by the process with organic material

Definitions

  • the present invention relates to a cationic electrodeposition coating composition excellent in smoothness and end face coverage and a method for achieving both smoothness and end face coverage of a cationic electrodeposition coating film using the same.
  • the present invention also relates to a cationic electrodeposition coating composition excellent in smoothness and end face coverage, and in particular, a cationic electrodeposition coating composition excellent in smoothness and end face coverage blended with specific crosslinked resin particles, and
  • the present invention relates to a method for achieving both smoothness and end face coverage of a cationic electrodeposition coating film using the same.
  • Electrodeposition coating is a coating method performed by immersing an object to be coated in an electrodeposition coating composition and applying a voltage. In this method, even an object having a complicated shape can be painted in detail, and can be painted automatically and continuously, so that large and complex shapes such as automobile bodies can be formed. It is widely used as an undercoating method for objects to be coated.
  • Electrodeposition coating is a coating coating on an article, so it is naturally desirable that the painted surface be smooth.
  • the metal punched portion has an acute end surface, and the anticorrosion performance deteriorates unless the coating is sufficiently coated on the portion. Therefore, both surface smoothness and end face coverage are performances required for electrodeposition coatings.
  • surface smoothness is fluidized and smoothed by reducing the viscosity of the uncured coating during bake-curing, but end face coverage is obtained by preventing the viscosity of the uncured coating from decreasing. Is. In other words, end face coverage is required to suppress the sagging of the coating film during curing of the coating film and to leave the coating film on an acute edge surface. That is, smoothness and end face coverage are contradictory performances.
  • Patent Document 1 As a technique for examining the coating film viscosity of the electrodeposition coating film, there is a publication of Japanese Patent Application Laid-Open No. 2002-285077 (Patent Document 1), and the minimum coating film viscosity during the coating film curing process is between 30 and 150 PaS. An electrodeposition coating composition for electric wires characterized by the above is described! /, (Claim 3). Patent Document 1 describes that by adjusting the minimum coating viscosity in the coating curing process, it is possible to improve the edge coverage, etc., which prevents sagging during melting.
  • JP-A-6-65791 Patent Document 2
  • an anti-curing primer is applied to a surface of an uncured coating formed by applying a cationic electrodeposition coating, and an intermediate coating or top coating is further applied.
  • the cationic electrodeposition paint has a minimum melt viscosity of 10 4 to 10 8 cps when the coating film is cured. It is disclosed that this coating film can shorten the coating process because three layers are baked at a time, is excellent in edge cover property, and the formed multilayer coating film is excellent in finishing strength and chipping resistance. Yes.
  • the finish and edge cover properties in a multilayer coating are disclosed.
  • Low ash differentiation has recently been promoted for electrodeposition paints.
  • Low ash differentiation is to reduce the amount of solid components with high specific gravity, such as inorganic pigments, and to prevent precipitation in the solid content of the electrodeposition paint.
  • the low ash differentiation reduces the energy and labor that has been used to stir the electrodeposition bath to prevent sedimentation. Therefore, if the content of the inorganic pigment that meets the above-mentioned requirements for low ash differentiation is decreased, the amount of resin in the paint will be relatively increased, and the viscosity of the uncured coating film obtained by electrodeposition coating will be increased. It cannot be increased appropriately, and as a result, the sagging control at the end face portion cannot be adjusted appropriately, and the end face coverage is reduced.
  • the current cationic electrodeposition paint uses a solid content concentration of around 20% by weight, so after electrodeposition coating, it is washed in several stages and is unnecessary for the object to be coated. After the electrodeposition paint attached to the surface, especially its solid content, is completely removed, the baking process is performed. For this reason, a large amount of washing water is used, and the water washing process becomes longer. Recently, it has been desired to reduce these washing water and shorten the washing process. As a means for shortening such a washing step, so-called low solid differentiation that further lowers the solid content concentration of 20% by weight in the paint is required. If this low solidification is performed simply, the solid content in the electrodeposition paint tends to settle due to a decrease in the viscosity of the paint.
  • the electrodeposition bath must be agitated, making it difficult to reduce the energy load.
  • it is possible to control the viscoelasticity so that the sedimentation of the paint can be prevented and the end face coverage can be easily performed even with low solidification, and the surface smoothness.
  • JP 2002-212488 A emulsifies an ⁇ , ⁇ ethylenically unsaturated monomer mixture using an acrylic resin having an ammonium group as an emulsifier for the purpose of improving the anti-mold property of the edge portion.
  • a cationic electrodeposition coating composition containing a crosslinked resin particle obtained by polymerization is disclosed.
  • the resin particles obtained here also have a small particle size of 0.05 to 0.3111.
  • cross-linked resin particles having a force average particle size of 1.0 m or less are blended in the electrodeposition paint, the smoothness of the resulting coating film is lowered.
  • Patent Document 1 Japanese Patent Laid-Open No. 2002-285077
  • Patent Document 2 JP-A-6-65791
  • Patent Document 3 JP 2005-23232 Koyuki
  • Patent Document 4 Japanese Patent Laid-Open No. 2002-212488
  • an object of the present invention is to provide a method for achieving both surface smoothness, end face coverage, and contradictory performance in a cationic electrodeposition coating.
  • the coating material is prevented from settling, and the strength and surface smoothness of the cationic electrodeposition coating material are also reduced.
  • the object is to provide a method that achieves compatibility, end face coverage, and conflicting performance.
  • the present invention is a cationic electrodeposition coating composition, and a storage elastic modulus (G) of an uncured deposited coating obtained by electrodeposition coating of the cationic electrodeposition coating composition (G ') is a 80 ⁇ 500dyn / cm 2, 80.
  • the cationic electrodeposition coating composition comprises a cationic epoxy resin, a block isocyanate curing agent, and, if necessary, resin particles (preferably crosslinked resin particles) and / or a pigment (preferably inorganic pigment).
  • resin particles preferably crosslinked resin particles
  • a pigment preferably inorganic pigment
  • the present invention provides an uncured deposition of a cationic electrodeposition coating material in a method for forming a cationic electrodeposition coating film by immersing an object to be coated in a cationic electrodeposition coating composition and applying a voltage.
  • a storage elastic modulus (G ′) at 140 ° C. to 80 to 500 dyn / cm 2
  • the loss elastic modulus (G ′′) at 80 ° C. to 10 to 150 dyn / cm 2
  • Provided is a method for achieving both smoothness and end face coverage of a cathodic electrodeposition coating film.
  • the storage elastic modulus and the loss elastic modulus are preferably adjusted by adding cross-linked resin particles or blending an inorganic pigment.
  • the average particle diameter is preferably 1.0 to 3.0 111.
  • the addition amount is preferably 3 to 15% by weight in the resin solid content of the cationic electrodeposition coating composition.
  • the adjustment of the storage elastic modulus and the loss elastic modulus with the inorganic pigment is preferably performed by blending the inorganic pigment in an amount of 10 to 20% by weight in the solid content of the cationic electrodeposition coating composition.
  • the storage elastic modulus and loss elastic modulus of both the inorganic pigment and the crosslinked resin particles can be adjusted.
  • the crosslinked resin particles have an average particle diameter of 1.0 to 3. Om, and the inorganic pigment is It is preferable to use it in an amount of 0.5 to 10% by weight in the solid content of the cathodic electrodeposition coating composition!
  • the crosslinked resin particles are contained in an amount of 3 to 15% by weight in the resin solid content of the cationic electrodeposition coating composition. It is preferable to be blended with.
  • the present invention has an average particle size of 1.0 to 3. O ⁇ m and a thermal softening temperature of 120 to 18;
  • a cationic electrodeposition coating composition containing cross-linked resin particles at 0 ° C. and having excellent smoothness and end face coverage.
  • the crosslinked resin particles are preferably 3 to 3% of the resin solid content of the cationic electrodeposition coating composition.
  • the cationic electrodeposition coating composition of the present invention has a low solid content that contains no inorganic pigment in the composition or contains an inorganic pigment at 7% by weight or less in the solid content of the cationic electrodeposition coating composition.
  • the type and low ash type are preferred!
  • the cationic electrodeposition coating composition of the present invention preferably has a solid content concentration of 0.5 to 9% by weight.
  • the crosslinked resin particles preferably include suspension polymerization, emulsion polymerization, etc., of the compound (a) having two or more unsaturated double bonds in the molecule and (meth) acrylate (b). Can be obtained using known methods.
  • the storage elastic modulus (G ′) at 140 ° C. of an uncured deposited coating film obtained by electrodeposition coating with a cationic electrodeposition coating composition is 80 to 500 dyn / cm 2 .
  • the loss elastic modulus (G ") at 80 ° C is from 10 to 150 dyn / cm 2 .
  • the present invention further provides a cationic electrodeposition-cured coating film having an Ra value of 0.25, im or less indicating the smoothness of the coating film obtained by curing the cationic electrodeposition coating composition.
  • the present invention also relates to a method for forming a cationic electrodeposition coating film by immersing an object to be coated in a cationic electrodeposition coating material and applying a voltage, with an average particle size of 1.0 to 3.O.
  • a method for achieving both the smoothness and the end face coverage of a cationic electrodeposition coating film which comprises blending crosslinked resin particles having a thermal maturation temperature of 120 to 180 ° C. with a cationic electrodeposition coating composition. provide.
  • the present invention relates to a method for forming an electrodeposition coating film using a low ash type and low solid content type cationic electrodeposition coating composition, wherein the average particle size is 1.0 to 3. O ⁇ m. And crosslinked resin particles having a thermal softening temperature of 120 to 180 ° C.
  • the storage modulus (G ') of the uncured deposited coating film at 140 ° C is 80-500 dyn / cm 2
  • the loss modulus at 80 ° C (G ")" Is adjusted to 10 to 150 dy n / cm 2 to provide a method for forming a cationic electrodeposition coating film with improved smoothness and end face coverage.
  • smoothness and end face coating can be achieved by simultaneously adjusting the loss elastic modulus G "and the storage elastic modulus G '.
  • smoothness has been ensured only by controlling the minimum melt viscosity by controlling the complex viscosity * in dynamic viscoelasticity measurement.
  • the loss elastic modulus: G "(viscosity term) was controlled to a specific range.
  • the loss elastic modulus G " is controlled within a specific range and the storage elastic modulus is simultaneously controlled in order to ensure both smoothness and end face coverage of the electrodeposition coating film, which has been regarded as a reciprocal event.
  • G 'to a specific range and assuming that G "and G' are independent parameters, the electrodeposition obtained by controlling these parameters to a specific range respectively. This achieves both smoothness of the coating film and end face coverage.
  • both surface smoothness and end face coverage can be achieved by controlling only the loss elastic modulus and storage elastic modulus of the uncured coating film deposited during electrodeposition! It is possible to provide a useful performance inspection or performance management method for cationic electrodeposition paints.
  • crosslinked resin particles having an average particle size of 1.0 to 3. O ⁇ m and a thermal softening temperature of 120 to 180 ° C are blended in the cationic electrodeposition paint. This makes it possible to achieve both surface smoothness and end face coverage.
  • a low ash type cationic electrodeposition coating composition since it is not possible to obtain an increase in the viscosity of the coating film due to the inorganic pigment, it is expected that the end face coverage will be deteriorated.
  • the end face coverage is also improved, and the coating performance of the low ash type cationic electrodeposition paint composition is improved. It is effective as a means of maintaining or improving.
  • the low ash type cationic electrodeposition coating composition means that the solid content of the cationic electrodeposition coating composition does not contain any inorganic pigment, or even if it is included, the maximum is 7% by weight in the coating solid content. It means that.
  • the present invention provides a low solid content type cationic electrodeposition coating composition that is more excellent in anti-settling ability than conventional ones and that can achieve both surface smoothness and end face coverage as described above. To do.
  • the low solid content type cationic electrodeposition coating composition means that the solid content concentration of the cationic electrodeposition coating composition is lower than the conventional 20 wt%, specifically 0.5 to 9 wt%. means.
  • the compatibility between surface smoothness and end face coverage can be correlated with the measurement of dynamic viscoelasticity of a deposited electrodeposition coating film obtained by electrodeposition coating.
  • the loss elastic modulus G "at 80 ° C and the storage elastic modulus G 'at 140 ° C are within the specified range, that is, the loss elastic modulus at 80 ° C is 10 ⁇ ; 150 dyn / cm 2 , 140 °
  • the storage elastic modulus G ′ in C when the surface elasticity is 80 to 500 dyn / cm 2 , both surface smoothness and cross-sectional coverage can be achieved.
  • the average particle diameter is 1.0 to 3. It was found that crosslinked resin particles having an O ⁇ m and a thermal softening temperature of 120 ° C or higher were blended in the cationic electrodeposition paint.
  • FIG. 1 is a graph showing the behavior of loss modulus (G ) value in dynamic viscoelasticity of five types of paints.
  • FIG. 2 is a graph showing the behavior of storage elastic modulus (G ′) values in the dynamic viscoelasticity of five types of paints.
  • FIG. 3 A graph showing the behavior of the complex viscosity (7) * value in the dynamic viscoelasticity of five types of paint.
  • FIG. 4A is a graph showing the relationship between the storage elastic modulus (G ′) of some paints at 80 ° C. and the electrodeposited skin.
  • FIG. 4B A graph showing the relationship between the complex viscosity of some paints at 80 ° C (7) * and the electrodeposition skin.
  • FIG. 4C A graph showing the relationship between the loss elastic modulus (G ") of some paints at 80 ° C and the electrodeposited skin.
  • FIG. 5A Draft showing the relationship between storage elastic modulus (G ') at 140 ° C and electrodeposition skin of some paints.
  • FIG. 5B Draft showing the relationship between the complex viscosity of some paints at 140 ° C (7) *) and the electrodeposition skin.
  • FIG. 5C Draft showing the relationship between the loss modulus (G ") of some paints at 140 ° C and the electrodeposited skin.
  • FIG. 6A A graph showing the relationship between the storage elastic modulus (G ') of some paints at 80 ° C and the end face coverage.
  • FIG. 6B This is a graph showing the relationship between the complex viscosity at 80 ° C (7) * and the end face coverage of several paints.
  • FIG. 7A is a graph showing the relationship between storage elastic modulus (G ′) at 140 ° C. and end face coverage of several paints.
  • FIG. 7B This is a graph showing the relationship between the complex viscosity (140) at 140 ° C and end face coverage of several paints.
  • FIG. 7C is a graph showing the relationship between the loss elastic modulus (G ”) and end face coverage of some paints at 140 ° C.
  • FIG. 8 is a graph showing the relationship between the temperature and the storage elastic modulus G ′ for explaining the thermal softening temperature.
  • FIG. 9 is a diagram schematically showing a 30 micron site from the tip of the cutter knife.
  • Dynamic viscoelasticity is an elastic modulus observed when a vibration (periodic) strain or force is applied to a linear viscoelastic body, and is related to frequency and temperature.
  • the following descriptions on dynamic viscoelasticity include: lecture rheology (edited by the Japan Society of Rheology), Chapter 2 Rheology of Polymer Liquids, p31-39 and Introduction to Polymer Chemistry (Seizo Okamura, Akio Nakajima, Shigeharu Onoki, This is based on the contents described in pp. 49-155, Chapter 4 Properties of Polymers, Viscoelasticity, by Nishijima Ankai IJ, Toshinobu Higashimura, and Norio Ise).
  • Stress and strain at the angular velocity ⁇ (2 ⁇ X frequency f) are given by the following equations.
  • J heart force ⁇ U) ⁇ e dvn / cm
  • both smoothness and end face coverage can be achieved by separately treating the viscosity and elasticity and controlling them.
  • the uncured coating film is dominated by the viscosity term in the initial stage of baking and is greatly affected by the loss modulus G ".
  • the uncured coating film melts.
  • the elastic term dominates thereafter and is greatly influenced by the storage elastic modulus G '.
  • the relationship between the loss modulus G "(viscosity term) and the storage modulus G '(elastic term) of the viscoelastic behavior in is the temperature at which the loss modulus G" ⁇ storage modulus G'. It means a point that changes from dominance to elasticity term dominance.
  • the loss elastic modulus G "at a temperature below the gel point (80 ° C) is controlled, and the storage elastic modulus at a temperature above the gel point (140 ° C). Smoothness and end face coating by controlling G '
  • the present inventors have found that the compatibility of the properties can be achieved and have completed the present invention.
  • V the viscoelastic behavior was measured with several paints, specifically, conventional paint systems containing pigments, those without them, and those with various crosslinked resin particles.
  • the viscosity starts to decrease from 40 to 80 ° C, and the viscosity increases slightly between 80 and 100 ° C, and greatly decreases when the temperature exceeds 100 ° C.
  • the curing reaction starts and the viscosity starts to increase again and gradually increases to around 150 ° C, and then the viscosity rapidly increases and the curing is completed.
  • we measured five types of paint! / Measured using Rheosol-G3000 from UBM Co., Ltd.
  • Resin particles 1 with “Pigment free” and crosslinked resin particles (average particle size; ! ⁇ 3 ⁇ m), 15% by weight of “Resin Particle 2”, “Pigment fr ee ”, 5% by weight of cross-linked resin particles (average particle diameter lOOnm), “Resin Particle 3” Is a blend of 10% by weight of “pigment free” crosslinked resin particles (average particle diameter lOOnm) different from the crosslinked resin particles used in “resin particle 2”.
  • PN-310 (Cation Electrodeposition Paint made by Nippon Paint Co., Ltd.) and PN-310 paint with a changed amount of inorganic pigment component, inorganic pigment component is removed from PN-310!
  • Several types of resin particles with different types and blending amounts were prepared and their viscous behavior was measured. From the results of viscoelasticity, Fig. 4 shows three viscoelastic behaviors at 80 ° C, namely G 'value and electrodeposited skin (Fig. 4A), 7] * value, so that changes at each temperature can be easily understood.
  • the electrodeposited skin (Fig. 4B) and G "value and the electrodeposited skin (Fig. 4C) are all displayed, and Fig.
  • Electrodeposited skin was represented by surface roughness (Ra).
  • the electrodeposited skin evaluated here means the appearance of the electrodeposited coating film, which will be described later, that is, smoothness, and is indicated by the measured value of the arithmetic average roughness (Ra) of the roughness curve. That is, by looking at the above-mentioned smoothness on the electrodeposited skin, the relationship between the electrodeposited skin and the viscous behavior was observed.
  • the present invention uses a loss elastic modulus (G ") of 80 ° C for electrodeposited skin (smoothness) and a storage elastic modulus (G of 140 ° C for end face coverage).
  • G loss elastic modulus
  • G storage elastic modulus
  • G loss elastic modulus
  • the storage elastic modulus (G,) is 90 to 500 dyn / cm 2 , more preferably 100 to 500 dyn / cm 2
  • the loss elastic modulus (G ′′) at 80 ° C. is preferably 10 to; 120 dyn / cm 2 , more preferably 10 to 100 dyn / cm 2 .
  • the storage elastic modulus G ' is less than the desirable lower limit, the end face coverage of the obtained electrodeposition coating film may be deteriorated, and when the desirable upper limit is exceeded, smoothness may be decreased. If the loss elastic modulus G "is below the desirable lower limit, the smoothness is improved, but the end face coverage of the resulting electrodeposition coating film may be deteriorated, and if it exceeds the desirable upper limit, the smoothness may be decreased.
  • the storage elastic modulus G 'and the loss elastic modulus G "described above are the elastic moduli of the uncured deposited coating, and the uncured is an electrodeposition coating of a cationic electrodeposition paint. Precipitation coating film obtained in this way It is still baked and cured.
  • the composition for cationic electrodeposition coating is added or blended with crosslinked resin particles and / or inorganic pigment.
  • an aqueous medium a cation that is dispersed or dissolved in the aqueous medium.
  • Binder resin containing a functional epoxy resin and a block isocyanate curing agent, a neutralizing acid, and an organic solvent.
  • the average particle diameter of the crosslinked resin particles is preferably 1.0 to 3. Om.
  • the average particle diameter of the crosslinked resin particles is preferably 1.0 to 3. Om.
  • the ratio of the surface area increases, and the interaction with the cationic epoxy resin, which is a binder resin component contained in the cationic electrodeposition coating composition, increases, resulting in precipitation. Since the viscosity of the coating film rises rapidly, it becomes difficult to adjust the viscoelastic behavior as described above.
  • the particle diameter is larger than 3. ⁇ , the smoothness decreases due to sedimentation without stirring of the electrodeposition paint and accumulation of particles on the horizontal surface during electrodeposition coating.
  • the crosslinked resin particles used in the present invention have a low ash and low solid content cationic electrodeposition coating composition! Is 1.0 to 3. O ⁇ m, and the thermal softening temperature is 120 ° C or higher, preferably 120 to 180 ° C.
  • the thermal softening temperature is 120 ° C or higher, preferably 120 to 180 ° C.
  • resin particles have an average particle diameter of less than 1.O ⁇ m. Most of them.
  • resin particles are simply blended to control the viscosity, so resin particles having an average particle size of less than 1.O ⁇ m are required.
  • the average particle size is larger than that of the prior art. It is preferable to mix the cross-linked resin particles having a squeezing force and a heat softening temperature of 120 ° C or higher, preferably from 120 to 1800 ° C! /.
  • the average particle size of the crosslinked resin particles used in the present invention is, as described above, a force of 1.0 to 3.O ⁇ m.
  • the lower limit is preferably 1 ⁇ 2111, more preferably 1 ⁇ 5 m.
  • the upper limit i is preferably 2. ⁇ ⁇ , more preferably 2 ⁇ 2 m.
  • Cross-linked resin particles having an average particle size greater than 3.0 0 111 suffer from a decrease in smoothness due to sedimentation when the electrodeposition coating is not stirred, or when the particles deposit on the horizontal surface during electrodeposition coating.
  • the average particle size here is measured by the following method.
  • the cross-linked resin particles used in the present invention have a heat softening temperature of 120 to 120 as described above in order to achieve both surface smoothness and end face coverage in a low ash and low solid content cationic electrodeposition coating composition. 180 ° C, but the upper limit is preferably 140 ° C, more preferably 160 ° C.
  • the heat softening temperature is lower than 120 ° C, the storage elastic modulus G ′ does not reach a predetermined value when an uncured electrodeposition coating film is baked, and the end face coverage cannot be secured.
  • the thermal softening temperature is a temperature at which the crosslinked resin particles start to soften. That is, G ′ at each temperature of the target bridge resin particle is obtained, and the temperature at the point where the change of G ′ rapidly changes with respect to the temperature change can be obtained in the following manner.
  • Crosslinking resin particle solid A sample obtained by adjusting the concentration of the part to 30% by weight was measured by measuring the temperature dependence using a rotary dynamic viscoelasticity measuring device Rhesol-G3000 (manufactured by UBM). Measure storage elastic modulus G 'from 90 ° C at 5 ° C, frequency 0.02Hz, temperature rise rate 4. Under the conditions of 0 ° C / min. The measurement results are as shown in the graph of Fig. 8. As is clear from FIG.
  • the storage modulus G ′ of the crosslinked resin particles maintains a constant viscosity in the initial temperature range (around 90 to 140 ° C. in FIG. 8), but at a certain temperature (140 ° C. in FIG. 8).
  • the temperature at the intersection is defined as the thermal softening temperature by drawing the tangent of the region where the viscosity is constant and the tangent of the region where the viscosity is decreasing.
  • the resin particles In order to increase the thermal softening temperature of the resin particles, it is necessary to increase the degree of crosslinking of the resin particles. In order to secure the thermal softening temperature region in the present invention, the resin particles need to be crosslinked resin particles.
  • the glass transition temperature is also an index indicating the softening of the resin. However, when the glass transition temperature (Tg) is measured on the cross-linked resin particles, it reaches a level of several hundred degrees (° C).
  • Tg glass transition temperature
  • the thermal softening temperature is used in the present invention because the thermal decomposition increases and the softening characteristics of the particles themselves cannot be measured.
  • the crosslinked resin particles have a crosslinked structure.
  • the value of the storage elastic modulus G ′ at 140 ° C. is less than 80 dyn / cm 2 , which is not preferable because end face coverage cannot be ensured.
  • the crosslinked resin particles are preferably used in an amount of 3 to 15% by weight in the resin solid content of the cationic electrodeposition coating composition. If the content of the crosslinked resin particles is less than 3 ⁇ 4% by weight, it becomes difficult to achieve both surface smoothness and end face coverage, and if it exceeds 15% by weight, the coating performance such as corrosion resistance may be deteriorated.
  • the above-mentioned “resin solid content” means the solid weight of all resin components (including crosslinked resin particles) contained in the cationic electrodeposition coating composition.
  • the content of the crosslinked resin particles in the present invention is low in ash and low solid content type cationic electrodeposition coating composition, so that both surface smoothness and end face coverage are compatible.
  • the force is preferably 3 to 15% by weight.
  • the lower limit is preferably 4% by weight, more preferably 5% by weight.
  • the upper limit is preferably 10% by weight, more preferably 8% by weight.
  • the average particle size of the crosslinked resin particles is 1.0 to 3.0 m
  • the crosslinked resin particles are not particularly limited, and for example, resin particles made of a resin having a crosslinked structure obtained mainly from an ethylenically unsaturated monomer, and resin particles made of an internally crosslinked urethane resin. To mention fine resin particles made of internally cross-linked melamine resin, the force S is used.
  • the resin having a crosslinked structure obtained mainly from the ethylenically unsaturated monomer is not particularly limited, and includes, for example, a crosslinkable monomer as an essential component and an ethylenically unsaturated monomer.
  • the monomer dissolves but the polymer does not dissolve, such as low SP organic solvents or high SP organic solvents such as esters, ketones, and alcohols.
  • the ethylenically unsaturated monomer is not particularly limited, and examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate.
  • Alkylesterol of acrylic acid or methacrylic acid such as 2-ethylhexyl (meth) acrylate; styrene, ⁇ -methylstyrene, butyltoluene, t-butylstyrene, ethylene, propylene, vinylinole acetate, bininole propionate, acrylonitrile, Examples include mettalylonitrile and dimethylaminoethyl (meth) acrylate.
  • the ethylenically unsaturated monomers may be used in combination of two or more.
  • the crosslinkable monomer is not particularly limited, and examples thereof include a monomer having two or more radically polymerizable ethylenically unsaturated bonds in the molecule and a group capable of reacting with each other. And two types of ethylenically unsaturated group-containing monomers.
  • the monomer having two or more radically polymerizable ethylenically unsaturated groups in the molecule that can be used for the production of the internally crosslinked fine resin particles is not particularly limited.
  • the combination of the functional groups reacting with each other present in the monomer having two types of ethylenically unsaturated groups, each carrying a group capable of reacting with each other is not particularly limited.
  • a combination of glycidinore acrylate and the like can be mentioned. Of these, a combination of an epoxy group and a carboxyl group is more preferable.
  • the resin particles comprising the internally crosslinked urethane resin are formed by reacting a polyisocyanate component with a diol having a hydroxyl group at the terminal and a diol having a carboxyl group or an active hydrogen-containing component having a triol.
  • An isocyanate end group-containing polyurethane prepolymer having an acid salt in the side chain is continuously added, and active hydrogen is contained. It is a fine resin particle composed of a polyurethane polymer obtained by reacting with a chain extender.
  • the polyisocyanate component used in the prepolymer is diphenylmethane 4, 4 'isocyanate; hexamethylene diisocyanate, 2, 2, 4 trimethyl hexane diisocyanate, or other aliphatic diisocyanates; Xanthenediisocyanate, 1 isocyanato 3-toisocyanatomethyl-3, 5 trimethylcyclohexane (isophorone diisocyanate), 4, 4'-dicyclohexylmethane diisocyanate, methylcyclodiylene diisocyanate, etc.
  • the polyisocyanate component is more preferably hexamethylene diisocyanate or isophorone diisocyanate.
  • the diol having a hydroxyl group at the terminal is not particularly limited, and examples thereof include a polyester resin having a molecular weight of 100 to 5,000, a polyester resin, a polycarbonate resin, and a polycarbonate resin.
  • the diol having a hydroxyl group at the terminal is not particularly limited, and examples thereof include polyethylene glycol, polypropylene glycol, polytetramethylene glycolate, polybutylene adipate, polyhexamethylene adipate, polyneopentinorea dipate, and polystrength prolatatone diol. And poly-3-methylvalerolatatondiol, polyhexamethylene carbonate, and the like.
  • the carboxyl group-containing diol is not particularly limited, and examples thereof include dimethylolacetic acid, dimethylolpropionic acid, and dimethylolbutyric acid. Of these, dimethylolpropionic acid is preferable.
  • the triol is not particularly limited, and examples thereof include trimethylolpropane, trimethylolethane, glycerin polystrength prolataton triol, and the like.
  • triol the inside of urethane resin particles takes a cross-linked structure.
  • the fine resin particles composed of the internally cross-linked melamine resin are not particularly limited.
  • the melamine resin and the polyol are dispersed in water in the presence of an emulsifier, and then dispersed in the particles formed by the dispersion.
  • examples thereof include internally cross-linked melamine resin particles obtained by performing a cross-linking reaction between a polyol and a melamine resin.
  • the melamine resin is not particularly limited, and examples thereof include G, Tree, Tetra, Pentahexer methylol melamine and alkyl etherated products thereof (alkyl is methyl, ethyl, propyl, isopropyl, butyl, isobutynole) and the like. The ability to raise S.
  • Examples of the melamine resin that are commercially available include Cymel 303, Simenore 325, and Cymenole 156 manufactured by Mitsui Cytec.
  • the polyol is not particularly limited, and examples thereof include triol having a molecular weight of 500, 3000, tetrolol and the like. Polyol ether triol and polyethylene ether triol are more preferred as the polyol.
  • the above-mentioned crosslinked resin particles are obtained by isolating finely crosslinked resin particles by a method such as mouth-mouthing, spray drying, freeze drying, etc., and pulverizing them to an appropriate particle size using a mill or the like. Even if it is used in a state, the obtained aqueous dispersion may be used as it is or after replacing the medium by solvent replacement.
  • the amount of inorganic pigment is 10 20 wt% (hereinafter sometimes referred to as "PWC") in the solid content of the cationic electrodeposition coating composition.
  • PWC 10 20 wt%
  • the PWC is more than 20% by weight and not more than 25% by weight, and the strength of the PWC that cannot achieve both smoothness and end face coverage is 10 to 20% by weight. It is possible to achieve both of these performances by using the above.
  • PWC refers to the ratio of the resin component and pigment component contained in the cationic electrodeposition coating composition to the solid content.
  • the PWC of the inorganic pigment is less than 10% by weight, the resin content will increase, and the resin will soften as the temperature rises, so the desired high viscosity cannot be obtained. Can not do it.
  • the PWC exceeds 20% by weight, the amount of pigment increases, and the fusing effect of the resin cannot be obtained. As a result, the high viscosity is not exhibited, and it becomes difficult to control the viscoelasticity.
  • the force S that PWC affects the viscous behavior, and its particle size does not significantly affect the viscous behavior.
  • the inorganic pigment used here is not particularly limited as long as it is a pigment usually used in an electrodeposition coating composition.
  • pigments include commonly used inorganic pigments, e.g. colored pigments such as titanium white and bengara; kaolin, talc, aluminum silicate, charcoal Extender pigments such as calcium phosphate, myrtle and clay; zinc phosphate, iron phosphate, anolenium phosphate, calcium phosphate, zinc phosphite, zinc cyanide, zinc oxide, aluminum tripolyphosphate, zinc molybdate, molybdic acid
  • examples include aluminum, calcium molybdate, aluminum phosphomolybdate, zinc aluminum phosphomolybdate, bismuth compounds, and antifungal pigments such as cerium compounds.
  • a third method for adjusting the viscoelastic behavior is to use the crosslinked resin particles and an inorganic pigment in combination.
  • the average particle diameter of the crosslinked resin particles is 1.0 to 3.0, and the amount used is 3 to 15% by weight in the solid content of the paint.
  • the amount of inorganic pigment used can be reduced in the solid content of the cationic electrodeposition coating composition (PWC) O. 5 to 10% by weight.
  • the lower limit is preferably 1% by weight, more preferably 2% by weight.
  • the upper limit is preferably 7% by weight, more preferably 5% by weight. If it is used in an amount exceeding 10% by weight, the amount of pigment will increase more than necessary, and the horizontal appearance may deteriorate due to sedimentation of the pigment. On the other hand, if it is less than 0.5% by weight, the color hiding property may be lowered.
  • the amount of the inorganic pigment can be further reduced, and as a result, reduction of energy and labor for preventing sedimentation of the solid content of the electrodeposition paint is expected. it can.
  • the viscoelastic behavior is adjusted using only crosslinked resin particles without using inorganic pigments, it is possible to greatly reduce the energy and labor for preventing sedimentation of the solid content. If inorganic pigments are not included! / Or include! / Even in very small amounts, the objects to be coated are washed with water after electrodeposition coating, but the washing process is greatly shortened. A great effect can be achieved, such as simplification of equipment and reduction of resource use.
  • the composition for cationic electrodeposition coating composition contains an aqueous medium, a power to disperse in the aqueous medium, or a binder resin containing a dissolved cationic epoxy resin and a block isocyanate curing agent, a neutralizing acid, and an organic solvent. .
  • the cationic electrodeposition coating composition may further contain an inorganic pigment, but the amount thereof is preferably 7% by weight or less based on the solid content of the cationic electrodeposition coating composition. As mentioned above, when promoting low ash differentiation, it is better not to include inorganic pigments. Good.
  • the specific crosslinked resin particles are added to the cationic electrodeposition coating composition. You may mix
  • the cationic epoxy resin used in the present invention includes an epoxy resin modified with amine.
  • Cationic epoxy resins typically have the ability to open with active hydrogen compounds that can introduce cationic groups into all of the epoxy rings of bisphenol type epoxy resins, or some epoxy rings to other It is produced by opening a ring with an active hydrogen compound and opening the remaining epoxy ring with an active hydrogen compound capable of introducing a cationic group.
  • a typical example of the bisphenol type epoxy resin is a bisphenol A type epoxy resin or a bisphenol F type epoxy resin.
  • the former commercial product YD-7011R (manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 460 to 490), Epicot 828 (manufactured by Yuka Shell Epoxy, epoxy equivalent 180 to 190), Epico Epoxy equivalent 450-500), Epico pancake 0 (same as epoxy equivalent 3000-4000), etc., and the latter commercially available products such as Epicoat 807, (epoxy equivalent 170).
  • R is a residue obtained by removing / resolving the glycidyloxy group of the diglycidyl epoxy compound
  • R ′ is a residue obtained by removing the isocyanate group of the diisocyanate compound
  • n is a positive integer.
  • An oxazolidone ring-containing epoxy resin represented by the above formula may be used as a cationic epoxy resin. This is because a coating film having excellent heat resistance and corrosion resistance can be obtained.
  • a block isocyanate curing agent blocked with a lower alcohol such as methanol and a polyepoxide are heated and kept in the presence of a basic catalyst to produce a by-product.
  • an epoxy resin containing an oxazolidone ring can be obtained by reacting a difunctional epoxy resin and a diisocyanate blocked with a monoalcohol (ie, bisurethane).
  • a difunctional epoxy resin ie, bisurethane
  • a diisocyanate blocked with a monoalcohol ie, bisurethane
  • Specific examples and production methods of this oxazolidone ring-containing epoxy resin are described in, for example, paragraphs 0012 to 0047 of JP-A-2000-128959 and are publicly known.
  • epoxy resins may be modified with an appropriate resin such as polyester polyol, polyether polyol, and monofunctional alkylphenol. Epoxy resins also have the ability to extend the chain using the reaction of epoxy groups with diols or dicarboxylic acids.
  • epoxy resins are active hydrogen compounds such that after ring opening, an amine equivalent of 0.3-3 Omeq / g is obtained, and more preferably 5-50% of them are occupied by primary amino groups. It is desirable to open the ring at.
  • the active hydrogen compound into which a cationic group can be introduced includes primary amines, secondary amines, tertiary amine acid salts, sulfides and acid mixtures.
  • primary amine, secondary amine, or tertiary amine acid salts are used as active hydrogen compounds capable of introducing cationic groups.
  • Specific examples include butylamine, octylamine, jetylamine, dibutylamine, methylbutyramine, monoethanolamine, diethanolamine, N-methylethanolamine, triethylamine hydrochloride, N, N dimethyl monoethanolamine acetate, jetyl disulfide
  • secondary amines that are blocked from primary amines such as ketimine of aminoethylethanolamine and diketimine of diethylenetriamine.
  • Amines can be used in combination of several types.
  • the polyisocyanate for obtaining the block isocyanate curing agent of the present invention refers to a compound having two or more isocyanate groups in one molecule.
  • the polyisocyanate may be, for example, any of aliphatic, alicyclic, aromatic and aromatic aliphatic.
  • Specific examples of polyisocyanates include aromatic diisocyanates such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), p-phenylene diisocyanate, and naphthalene diisocyanate.
  • aliphatic diisocyanates such as hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexane diisocyanate, lysine diisocyanate and the like; -Cyclohexane diisocyanate (CDI), isophorone diisocyanate (IPDI), 4,4'-dicyclohexylenomethane diisocyanate (hydrogenated MDI), methylcyclohexane diisocyanate, isopropylidene Cyclohexyl, 4,4'-diisocyanate, and 1,3-diisocyanatomethylcyclohexane (hydrogenated XDI), hydrogenated TDI, 2,5- Aliphatic diisocyanates having 5 to 18 carbon atoms such as 2,6-bis (isocyanatomethyl) bibicyclo [2.2.1] heptane (also called norbornane diisocyanate); Aliphatic diisocyanates such
  • An adduct or prepolymer obtained by reacting a polyisocyanate with a polyhydric alcohol such as ethylene glycol, propylene glycol, trimethylolpropan or hexanetriol at an NCO / OH ratio of 2 or more is also cured with a block isocyanate. May be used in preparations.
  • a blocking agent is added to a polyisocyanate group and is stable at room temperature, but can regenerate a free isocyanate group when heated to a temperature higher than the dissociation temperature.
  • the use of a commonly used ⁇ -force prolatatam, ptylcete solve, or the like is performed with a force S.
  • crosslinked resin particles When used as a component of the cationic electrodeposition paint, they may be blended at any stage of producing the electrodeposition paint, but a method of adding directly to the produced cationic electrodeposition paint is preferable. good.
  • the electrodeposition coating composition used in the present invention may contain a commonly used inorganic pigment.
  • inorganic pigments include commonly used inorganic pigments, for example, colored pigments such as titanium white and bengara; extender pigments such as kaolin, talc, aluminum silicate, calcium carbonate, my strength and clay; zinc phosphate , Iron phosphate, aluminum phosphate, calcium phosphate, zinc phosphite, zinc cyanide, zinc oxide, aluminum tripolyphosphate, zinc molybdate, aluminum molybdate, calcium molybdate and aluminum phosphomolybdate, zinc aluminum phosphomolybdate
  • antibacterial pigments such as bismuth oxide, bismuth hydroxide, basic bismuth carbonate, bismuth nitrate and bismuth sulfate.
  • Such an inorganic pigment is 7% by weight or less, preferably 5% by weight or less, more preferably 3% by weight or less based on the solid content of the coating resin in the cationic electrodeposition coating composition.
  • the weight percent of this resin solids is also called PWC. If the inorganic pigment concentration exceeds 7% by weight, low ash differentiation cannot be achieved sufficiently, and the energy burden for preventing sedimentation will increase.
  • a pigment When a pigment is used as a component of an electrodeposition paint, generally, the pigment is dispersed in an aqueous medium at a high concentration in advance to form a paste (pigment dispersion paste). This is because the pigment is in a powder form and it is difficult to disperse it in a single step in a low concentration uniform state used in the electrodeposition coating composition. In general, such a paste is called a pigment dispersion paste!
  • the pigment dispersion paste is prepared by dispersing a pigment together with a pigment dispersion resin in an aqueous medium.
  • a pigment dispersion resin a cationic polymer such as a cationic or nonionic low molecular weight surfactant or a modified epoxy resin having a quaternary ammonium group and / or a tertiary sulfone group is generally used.
  • aqueous medium ion exchange water or water containing a small amount of alcohol is used.
  • the pigment-dispersed resin is used in an amount of a solid content ratio of 20 to 100 mass parts with respect to 100 mass parts of the pigment.
  • the pigment is dispersed using a normal dispersing device such as a ball mill or a sand grind mill until the particle size of the pigment in the mixture reaches a predetermined uniform particle size. Obtain a dispersion paste.
  • the cationic electrodeposition coating composition used in the present invention includes, in addition to the above components, organic tin compounds such as dibutyltin laurate, dibutyltin oxide, and dioctyltin oxide, N-methyl An amine such as lumorpholine, or a metal salt such as strontium, cobalt, or copper may be included as a catalyst. These can act as a catalyst for the dissociation of the blocking agent of the curing agent.
  • the concentration of the catalyst is preferably 0.;! To 6 parts by mass with respect to 100 solid parts by mass of the total of the cationic epoxy resin and the curing agent in the electrodeposition coating composition.
  • the cationic electrodeposition coating composition of the present invention comprises the above-described cationic epoxy resin, block isocyanate curing agent, and optionally crosslinked resin particles and / or pigment dispersion paste and catalyst. It can be prepared by dispersing in.
  • the aqueous medium contains a neutralizing acid in order to neutralize the cationic epoxy resin and improve the dispersibility.
  • the neutralizing acid is an inorganic or organic acid such as hydrochloric acid, nitric acid, phosphoric acid, formic acid, acetic acid, lactic acid, sulfamic acid, or acetylidaricin.
  • the aqueous medium in this specification is water or a mixture of water and an organic solvent.
  • organic solvents examples include hydrocarbons (eg, xylene or tonoleene), alcohols (eg, methyl alcohol, n-butyl alcohol, isopino pinoleanolenoconole, 2-ethylenohexenoreanonoleconole).
  • hydrocarbons eg, xylene or tonoleene
  • alcohols eg, methyl alcohol, n-butyl alcohol, isopino pinoleanolenoconole, 2-ethylenohexenoreanonoleconole.
  • Ethylene glycol, propylene glycol ethers (eg, ethylene glycol monoethyl ether, ethylene glycol monobutino enoate, ethylene glycol monohexeno enoate, propylene glycol eno enoenoate) , 3-methylolene 3-methoxybutanol monoole, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether), ketones (eg, methyl isobutyl ketone, cyclohexanone, isophorone, acetylacetone), Ethers (e.g., ethylene glycol monomethyl E chill ether acetate, ethylene glycol mono butyl ether acetate) or mixtures thereof.
  • ethers eg, ethylene glycol monoethyl ether, ethylene glycol monobutino enoate, ethylene glycol monohexeno enoate, propylene glycol eno enoeno
  • the cationic electrodeposition coating composition of the present invention may contain cross-linked resin particles.
  • the addition method may be any of the steps for producing the electrodeposition coating. It is preferable to add it directly to the produced cationic electrodeposition coating.
  • the amount of the block isocyanate curing agent reacts with active hydrogen-containing functional groups such as primary, secondary amino groups and hydroxyl groups in the cationic epoxy resin at the time of curing to give a good cured coating film.
  • active hydrogen-containing functional groups such as primary, secondary amino groups and hydroxyl groups in the cationic epoxy resin
  • It is generally in the range of 90/10 to 50/50, preferably 80/20 to 65/35, expressed as a weight ratio of solids to the curing agent (epoxy resin / curing agent).
  • the amount of neutralizing acid is that which is sufficient to neutralize at least 20%, preferably 30-60%, of the cationic groups of the cationic epoxy resin.
  • the organic solvent is indispensable as a solvent when preparing resin components such as a force thione epoxy resin and a block isocyanate curing agent, and a complicated operation is required for complete removal.
  • Examples of the organic solvent usually contained in the coating composition include ethylene glycol monobutyl etherol, ethylene glycol monohexenoleenotenole, ethylene glycol monoethylenohexenoxenoreethenole, and propylene glycolenolemonobutinorein.
  • Examples include tenole, dipropylene glycol monobutyl ether, propylene glycol monophenyl ether.
  • the cationic electrodeposition coating composition may contain commonly used coating additives such as a plasticizer, a surfactant, an antioxidant, and an ultraviolet absorber.
  • the cationic electrodeposition coating composition of the present invention When the cationic electrodeposition coating composition of the present invention is intended for low solid differentiation, its solid content concentration is 20% by weight or less.
  • the solid content concentration of the paint is preferably 0.5 to 9% by weight, and the lower limit thereof is preferably 2% by weight, more preferably 4% by weight.
  • the upper limit is preferably 7% by weight, more preferably 6% by weight. If the solid content concentration is less than 0.5% by weight, a normal coating film cannot be formed. If the solid content concentration is more than 9% by weight, the water washing process is shortened in the cationic electrodeposition coating line, which is the effect of low solid differentiation, and the equipment is reduced. It becomes impossible to obtain effects such as simplification.
  • the solid content concentration refers to the concentration in the coating of the total solid content weight of the pigment component and the resin component (including the crosslinked resin particle component) contained in the cationic electrodeposition coating composition. If the solid content is thus low, the conductivity of the cationic electrodeposition paint may be reduced. Therefore, it is preferable to add a conductivity control agent separately.
  • the conductivity control agent used in the present invention is not particularly limited as long as it is a material that adjusts the conductivity of the cationic electrodeposition paint to a desired range, but an amine value of S200 to 500 mmol / 100 g is used. What is comprised from the amino-group containing compound which has is preferable.
  • the conductivity control agent for cationic electrodeposition coating materials of the present invention is prepared so that the amine value is within the above range, any amino group-containing material may be used, but usually an amine-modified epoxy resin or an amine-modified acrylic resin is used. preferable.
  • the conductivity control agent for cationic electrodeposition paints of the present invention may be neutralized with an acid, if necessary.
  • the amine value is preferably 250 to 450 mmol / 100 g, and more preferably 300 to 400 mmol / 100 g. If the amine value is less than 200 mmol / 100 g, the necessary addition amount for adjusting the liquid conductivity of the low solid content cationic electrodeposition coating to the optimum value increases, which may impair the corrosion resistance. On the other hand, if it exceeds 500 mmol / 100 g, the precipitation property is lowered and the desired throwing power cannot be obtained. In addition, the suitability of the galvanized steel sheet also decreases.
  • the conductivity control agent is a compound having a low molecular weight to a high molecular amino group, and usually includes a high molecular weight compound such as a amine-modified epoxy resin or a amine-modified acrylic resin.
  • a high molecular weight compound such as a amine-modified epoxy resin or a amine-modified acrylic resin.
  • the low molecular weight amino group-containing compound include monoethanolamine, diethanolamine, and dimethylbutylamine.
  • the amine-modified epoxy resin can be obtained by modifying an epoxy group of an epoxy resin with an amine compound.
  • Epoxy resins can be used in general, but are bisphenol type epoxy resin, t-butylcatechol type epoxy resin, phenol nopolac type epoxy resin, cresol nopolac type epoxy resin, and molecular weight is 500-20000. Those having the following are preferred. Of these epoxy resins, phenol nopolac type epoxy resins and cresol nopolac type epoxy resins are both desirable. In particular, these epoxy resins are commercially available. Examples thereof include phenol nopolac type epoxy resin DEN-438 manufactured by Dow Chemical Japan, and taresol nopolak type epoxy resin YDCN-703 manufactured by Tohto Kasei Co., Ltd.
  • epoxy resins may be modified with a resin such as polyester polyol, polyether polyol, and monofunctional alkylphenol. Epoxy resins can also be chain-extended using the reaction of epoxy groups with diols or dicarboxylic acids.
  • a resin such as polyester polyol, polyether polyol, and monofunctional alkylphenol. Epoxy resins can also be chain-extended using the reaction of epoxy groups with diols or dicarboxylic acids.
  • the amine-modified acrylic resin for example, a homopolymer of dimethylaminoethyl methacrylate, which is an amino group-containing monomer, or a copolymer with another polymerizable monomer may be used as it is, or glycidyl methacrylate. It can be obtained by modifying the glycidyl group of a homopolymer of a rate or a copolymer with another polymerizable monomer with an amine compound.
  • Examples of the compound that introduces an amino group into an epoxy resin or an acrylic resin containing an epoxy group include primary amines, secondary amines, and tertiary amines. Specific examples thereof include butynoreamine, talented cutinoleamine, jetinoreamine, butinoreamine, dimethylenobutynoamine, monoethanolamine, diethanolamine, N-methylethanolamine, triethylamine hydrochloride, N, N-dimethylethanolamine.
  • primary amines such as aminoethylethanolamine diketimines and primary alkylamine blocked secondary amines such as diketimines of jetylhydroamine are listed.
  • a plurality of amines may be used.
  • the number average molecular weight of these amine-modified epoxy resins and amine-modified acrylic resins is preferably 500 to 20,000. If the number average molecular weight is less than 500, corrosion resistance may be impaired, and although the reason is not clear, a decrease in throwing power and a decrease in suitability for galvanized steel sheets are observed. If the number average molecular weight is greater than 20000 !, there is a risk of causing a decrease in the finished appearance.
  • Acids used for neutralization are inorganic acids or organic acids such as hydrochloric acid, nitric acid, phosphoric acid, sulfamic acid, formic acid, acetic acid, and lactic acid.
  • the cationic electrodeposition coating composition is electrodeposited on an object to form an electrodeposition coating film.
  • the material to be coated is not particularly limited as long as it is electrically conductive, and examples thereof include iron plates, steel plates, aluminum plates, those obtained by surface treatment thereof, and molded products thereof.
  • Electrodeposition of the cationic electrodeposition coating composition is usually carried out by applying a voltage of 50 to 450 V between the object to be coated as the cathode and the anode. If the applied voltage is less than 50V, electrodeposition is insufficient, and if it exceeds 450V, the coating is destroyed and the appearance becomes abnormal. During electrodeposition coating, the bath temperature of the coating composition is usually adjusted to 10 to 45 ° C.
  • the electrodeposition coating step includes a step of immersing an object to be coated in a cationic electrodeposition coating composition, and a step of applying a voltage between the above object to be coated as a cathode and an anode to deposit a film. Composed. The time for applying the voltage varies depending on the electrodeposition conditions. In general, the force is 2 to 4 minutes.
  • the film thickness of the electrodeposition coating film can be generally formed in the range of 5 to 2511 m. If the film thickness is less than 5 ⁇ m, the anti-mold property may be insufficient. If the film thickness exceeds 25 m, the film thickness is more than necessary to obtain the coating film performance.
  • the film resistance of the electrodeposition coating film is preferably 1000 to 1600 kQ / cm 2 at a film thickness of 15 111. Film resistance of the coating film is in a state that is not obtained sufficient electric resistance is less than 10 00k ⁇ / cm 2, there is a possibility that poor throwing, also more than 1600k ⁇ / cm 2 when the film appearance May be inferior.
  • the film resistance of the coating film is more preferably 1100-1500 kQ / cm 2 .
  • the film resistance value of the coating film can be obtained by the following formula from the residual current value (A) of the coating film at the final coating voltage (V).
  • the electrodeposition coating film obtained as described above is 120 to 260 after completion of the electrodeposition process, or after being washed with water.
  • C preferably 140-220. It is hardened by baking with C for 10 to 30 minutes to obtain a cured electrodeposition coating film.
  • the cured electrodeposition coating film of the present invention has an Ra value that is used for evaluation of surface smoothness with high surface smoothness, and is preferably 0.25 mm or less, more preferably 0.20 mm or less. is there. The lower limit is preferably zero.
  • the Ra value was measured in accordance with JIS-B0601 using an evaluation type surface roughness measuring machine (manufactured by Mitutoyo Corporation, SURFTEST SJ-201P). Ra value force S The smaller the roughness, the better the appearance of the coating film with less unevenness.
  • the cationic electrodeposition coating material in the method of forming a cationic electrodeposition coating film by immersing an object to be coated in the cationic electrodeposition coating material and applying a voltage, has an average particle size of 1.0.
  • a method for achieving both the smoothness and end face coverage of a cationic electrodeposition coating film characterized by containing crosslinked resin particles having a viscosity of ⁇ 3.0 m and a thermal softening temperature of 120 to 180 ° C.
  • the above-mentioned specific crosslinked resin particles are added to the cationic electrodeposition paint as an additive even in a low solid content type and low ash content type cationic electrodeposition paint.
  • the blending amount is 3 to 15% by weight based on the solid content of the cationic electrodeposition paint.
  • Hexamethylene diisocyanate trimer (Coronate HX: manufactured by Nippon Polyurethane Co., Ltd.) in a flask equipped with a stirrer, cooler, nitrogen injection tube, thermometer and dropping funnel
  • a flask equipped with a stirrer, cooler, nitrogen injection tube, thermometer and dropping funnel was charged with 382.20 parts of bisphenol A type epoxy resin (trade name DER—331J) with an epoxy equivalent of 188 and bisphenol A111.98 parts.
  • the sample was weighed, heated to 80 ° C., and uniformly dissolved. Then, 1 ⁇ 53 parts of a 2-ethyl-4-methylimidazole 1% solution was added and reacted at 170 ° C. for 2 hours. After cooling to 140 ° C, 196.50 parts of 2-ethylhexanol half-blocked isophorone diisocyanate (nonvolatile content 90%) was added and reacted until the NCO group disappeared.
  • This suspension was subjected to suspension polymerization for 5 hours at a stirring speed of 150 rpm and a reaction temperature of 81 to 83 ° C using a normal batch-type reaction vessel. After cooling, the obtained dispersion was 200 mesh. Filtration through a net gave non-crosslinked resin particles. The obtained non-crosslinked resin particle dispersion had a non-volatile content of 30% and an average particle size of 3 Hm.
  • a cationic electrodeposition coating composition having 5% by weight and a solid content of 5% by weight was obtained.
  • cross-linked resin particles cross-linked resin particles mainly composed of methyl methacrylate; manufactured by Toyobo Co., Ltd., Tuftic (ffi) F-200
  • crosslinked resin particles crosslinked resin particles mainly composed of methyl methacrylate; 84 parts of Tuftic (ffi) F-200, manufactured by Toyobo Co., Ltd.
  • cross-linked resin particles cross-linked resin particles mainly composed of methyl methacrylate; Toyobo Co., Ltd., Tuftic (ffi) F-200
  • crosslinked resin particles crosslinked resin particles mainly composed of styrene monomer; manufactured by Soken Chemical Co., Ltd., Chemisnow SX500H, average particle diameter 3 m
  • 40 parts crosslinked resin particles mainly composed of styrene monomer; manufactured by Soken Chemical Co., Ltd., Chemisnow SX500H, average particle diameter 3 m
  • the loss elastic modulus at 80 ° C, storage elastic modulus at 140 ° C, smoothness and end face coverage of dynamic viscoelasticity were determined by the following methods. Evaluation was performed.
  • a tin plate is dipped in the cationic electrodeposition paint obtained above, and an electrodeposition coating film is formed by coating at a coating voltage such that the film thickness after baking is ⁇ .
  • the electrodeposition paint composition was removed.
  • the uncured coating piece was immediately taken out without drying, and a sample was prepared.
  • the sample obtained in this manner was subjected to temperature-dependent measurement in dynamic viscoelasticity using a rotational dynamic viscoelasticity measuring device Rheosol-G3000 (manufactured by UBM). The measurement was performed at 5 deg and a frequency of 0.02 Hz.
  • the prepared sample was set and the measurement temperature was kept at 50 ° C. After the measurement was started, the viscosity of the coating film was measured when the electrodeposition coating film spread uniformly in the cone plate.
  • the appearance of the electrodeposition coating film was evaluated by measuring the arithmetic average roughness (Ra) of the roughness curve.
  • An uncured electrodeposition coating obtained by immersing a cold-rolled steel sheet treated with zinc phosphate in the cationic electrodeposition coating obtained above and coating it at a coating voltage such that the film thickness after baking is 15 m.
  • the membrane was baked at 160 ° C for 10 minutes. Thereafter, the Ra value of this cured electrodeposition coating film was measured using an evaluation type surface roughness measuring instrument (SURFTEST SJ-201P, manufactured by Mitutoyo Corporation) in accordance with JIS-B0601. 2.
  • a cationic knife electrodeposition coating composition is immersed in a coating material of a cutter knife (OLFA: LB 50K) that has been treated with zinc phosphate, and a voltage is applied between the coating material and the anode as a cathode. Deposit the film.
  • the electrodeposition conditions were applied voltage and time adjusted so that the deposited film thickness was ⁇ ⁇ ⁇ ⁇ ⁇ on the cutter knife.
  • the obtained electrodeposition coating film was washed with water and baked at 160 ° C. for 10 minutes to obtain a cured electrodeposition coating film.
  • Comparative Example 1A has a storage elastic modulus (G ′) that is out of the range of the present invention, and its end face coverage is not good.
  • 2A is a mixture of the crosslinked resin particles of Production Example 5A, but both the loss elastic modulus (G ") and storage elastic modulus (G ') are out of the scope of the present invention, and smoothness and end face coverage are also included. Not good.
  • Comparative Example 3A is also composed of the crosslinked resin particles of Production Example 5A, and the average particle diameter of the crosslinked resin particles used here is as small as lOOnm and loss modulus (G ")
  • the non-crosslinked particles are blended, and the value of the storage elastic modulus (G ′) is out of the range of the present invention.
  • Comparative Example 5A is outside the scope of the present invention in terms of the power loss elastic modulus (G ”) containing inorganic pigments instead of resin particles, and as a result, smoothness is poor. not good.
  • Example 1A contains the pigment of Production Example 4A, which falls within the scope of the present invention, and has excellent smoothness and end face coverage.
  • the storage elastic modulus (G ′) and the loss elastic modulus (G ′′) are controlled within the scope of the present invention by blending specific particles, and both smoothness and end face coverage are achieved. Both are excellent.
  • Hexamethylene diisocyanate trimer (Coronate HX: manufactured by Nippon Polyurethane Co., Ltd.) in a flask equipped with a stirrer, cooler, nitrogen injection tube, thermometer and dropping funnel
  • Production Example 2B Production of emulsion containing amine-modified epoxy resin and block isocyanate curing agent
  • MIBK methylisoptyl ketone
  • methinorethananolamine 37.5 parts
  • diethanolamine 52.5 parts
  • MIBK methylisoptyl ketone
  • 205 parts of cresol nopolac epoxy resin product name: YDCN-703, manufactured by Tohto Kasei Co., Ltd.
  • the molecular weight was measured and found to be 2,100.
  • the amine value (MEQ (B)) of the obtained amino-modified resin was measured and found to be 340 mmol / 100 g.
  • PWC 0%, resin particles 15% by weight, and solid content 5% by weight.
  • cross-linked resin particles cross-linked resin particles mainly composed of methyl methacrylate; Tofubo Co., Ltd., Tuftic (SW) F-200
  • SW Tuftic
  • crosslinked resin particles crosslinked resin particles mainly composed of styrene monomer; 38 parts by Chemisnow (ffi) SX130M, manufactured by Soken Chemical Co., Ltd.
  • the loss elastic modulus at 80 ° C and the storage elastic modulus at 140 ° C, smoothness and end face coverage, etc. in dynamic viscoelasticity were determined by the following methods. Evaluation was performed.
  • a tin plate is dipped in the cationic electrodeposition paint obtained above, and an electrodeposition coating film is formed by coating at a coating voltage such that the film thickness after baking is ⁇ .
  • the electrodeposition paint composition was removed.
  • the uncured coating piece was immediately taken out without drying, and a sample was prepared.
  • the sample obtained in this way was subjected to temperature-dependent measurement in dynamic viscoelasticity using Rheosol-G3000 (manufactured by UBM), a rotary dynamic viscoelasticity measuring device. Setting conditions: strain 0.5 deg, frequency 0
  • the storage elastic modulus (G ') and loss elastic modulus (G ”) were measured at 02Hz and the heating rate of 2.0 ° C / min.
  • the appearance of the electrodeposition coating film was evaluated by measuring the arithmetic average roughness (Ra) of the roughness curve.
  • An uncured electrodeposition coating film obtained by immersing a cold-rolled steel sheet treated with zinc phosphate in a cationic electrodeposition coating and applying a coating voltage that gives a film thickness of 15 / ⁇ 111 after baking. Bake for 10 minutes at ° C. Thereafter, the Ra value of the uncured electrodeposition coating film was measured using an evaluation type surface roughness measuring machine (SURFTEST SJ-201P, manufactured by Mitutoyo Corporation) in accordance with JIS-B0601. 2. Using a sample with a 5mm width cut-off (5 compartments), measure 7 times and Ra value was obtained by the average. The results are shown in Table 2 and Table 3. It can be said that the smaller the Ra value, the better the appearance of the coating film with less unevenness. Specifically, if the Ra value is less than 0.25 111, it is a pass.
  • a cold-rolled steel sheet treated with zinc phosphate is immersed horizontally in the cationic electrodeposition paints obtained in the production examples and comparative examples, and a coating voltage is applied so that the film thickness after baking is 15 m.
  • An uncured electrodeposition coating is obtained.
  • the arithmetic average of the roughness curve was used in the same manner as the above-described appearance evaluation of the electrodeposition coating film. Roughness (Ra) was measured.
  • a sample obtained by adjusting the cross-linked resin particles to a solid content concentration of 30% by weight was measured by temperature dependency measurement using Rheosol-G3000 (manufactured by UBM), which is a rotary dynamic viscoelasticity measuring device.
  • the storage elastic modulus G ′ was measured from 90 ° C under the measurement conditions of strain 0.5 deg., Frequency 0.02 Hz, and heating rate 4.0 ° C / min.
  • the measurement results are shown in a graph as shown in FIG. 8, and the tangent of the region where the viscosity is constant and the tangent of the region where the viscosity is lowered are drawn, and the temperature at the intersection is defined as the thermal softening temperature.
  • FIG. 9 schematically shows the 30-micron area from the tip of the cutter knife. If this film thickness is 7.8 111 or more, it passes.
  • the average particle diameter of the crosslinked resin particles used in the above examples and comparative examples was measured as follows.
  • the average particle size of the crosslinked resin particles was measured by a granular particle permeation measurement method using MICROTRAC9340UPA manufactured by Nikkiso Co., Ltd.
  • the solvent (water) refractive index 1.33 and the resin refractive index 1.59 were used.
  • Inorganic pigment amount (%) 0 0 3 0
  • the degree of cross-linking was expressed by thermal softening temperature based on thermal softening temperature measurement.
  • Degree of cross-linking thermal softening temperature of 120 ° C or more, less than 140 ° C
  • Crosslinked resin particles # 1 Crosslinked resin particles obtained in Production Example 5B
  • Crosslinked resin particles # 2 Chemisnow SX—130M (trade name) manufactured by Soken Chemical Co., Ltd.
  • Crosslinked resin particle # 3 GM — 0105 (trade name) manufactured by Ganz Kasei
  • Crosslinked resin particle # 4 Toyobo F-200 (trade name)
  • Comparative Example 1B which is an example of a conventional paint, excellent performance in smoothness and end face coverage was exhibited.
  • Comparative Example 1B contains a conventional inorganic pigment that does not contain resin particles, and has good surface smoothness and end face coverage, but its ash content (Ash content) is high, so its sedimentation evaluation is poor.
  • Comparative Example 2B does not contain inorganic pigments or resin particles, and has excellent smoothness S and end face coverage becomes very poor.
  • Comparative Examples 3B to 5B contain resin particles, but the particle size is small (Comparative Examples 3B and 4B), the force is! /, The thermal softening temperature is small! /, (Comparative Example 5B) is there. Comparative Examples 3B to 5B showed a tendency that both the end face coverage and the surface smoothness were not good.

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Abstract

L'invention concerne une composition de revêtement pour électrodéposition cationique qui permet d'obtenir par électrodéposition un revêtement non durci présentant un module de conservation (G') compris entre 80 et 500 dyn/cm2 à 140 °C et une perte d'élasticité (G”) comprise entre 10 et 150 dyn/cm2 à 80 °C ; ainsi qu'un procédé d'enduction avec la composition. Les valeurs de G' et G” peuvent être ajustées en ajoutant des particules de résine réticulées ayant une taille de particule moyenne comprise entre 1,0 et 3,0 μm et/ou un pigment inorganique à la composition de revêtement. La composition selon l'invention permet d'obtenir un film de revêtement par électrodéposition cationique présentant à la fois une excellente homogénéité de surface et un excellent recouvrement des faces de bord.
PCT/JP2007/070723 2006-10-25 2007-10-24 Composition de revêtement pour électrodéposition cationique et son application WO2008050797A1 (fr)

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AU2007310040A AU2007310040A1 (en) 2006-10-25 2007-10-24 Cationic electrodeposition coating composition and application thereof
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DE102010045149A1 (de) * 2010-09-11 2012-03-15 Bayer Material Science Ag Beschichtung auf Polyurethanbasis für Anzeigebereiche
EP3960821A4 (fr) * 2019-04-25 2023-01-25 Kansai Paint Co., Ltd Composition de revêtement pour électrodéposition cationique
WO2021123106A1 (fr) * 2019-12-19 2021-06-24 Basf Coatings Gmbh Pigment noir de fumée contenant des compositions de matériau de revêtement par électrodéposition
US20230220580A1 (en) * 2022-01-12 2023-07-13 General Electric Company Formation of a barrier coating using electrophoretic deposition of a slurry

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06287267A (ja) * 1993-04-07 1994-10-11 Kansai Paint Co Ltd カチオン電着性微粒子及びそれを含む電着塗料組成物
JP2003129001A (ja) * 2001-07-26 2003-05-08 Kansai Paint Co Ltd 塗膜の耐ハジキ性改良方法
JP2003213218A (ja) * 2001-11-15 2003-07-30 Kansai Paint Co Ltd 熱硬化性液状塗料組成物の塗膜平滑性改良方法
JP2005200506A (ja) * 2004-01-14 2005-07-28 Nippon Paint Co Ltd カチオン電着塗料組成物
JP2005200692A (ja) * 2004-01-14 2005-07-28 Nippon Paint Co Ltd カチオン電着塗膜の形成方法
WO2005068570A1 (fr) * 2004-01-14 2005-07-28 Nippon Paint Co., Ltd. Composition de revetement par electrodeposition cationique
JP2006257161A (ja) * 2005-03-15 2006-09-28 Nippon Paint Co Ltd カチオン電着塗料組成物、電着浴の管理方法および電着塗装システム

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5380781A (en) * 1992-07-27 1995-01-10 Kansai Paint Co., Ltd. Cationically electrodepositable fine particles derived from alkoxysilane-modified epoxy resins and cationic electrodeposition paint composition comprising the same
JP2001192611A (ja) * 2000-01-07 2001-07-17 Nippon Paint Co Ltd カチオン電着塗料組成物
DE10052438C2 (de) * 2000-10-23 2002-11-28 Basf Coatings Ag Verfahren zur Erzeugung einer Mehrschichtlackierung und deren Verwendung
US6635315B2 (en) * 2001-11-15 2003-10-21 Kansai Paint Co., Ltd. Method for improving smoothness of film formed from thermosetting liquid coating composition

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06287267A (ja) * 1993-04-07 1994-10-11 Kansai Paint Co Ltd カチオン電着性微粒子及びそれを含む電着塗料組成物
JP2003129001A (ja) * 2001-07-26 2003-05-08 Kansai Paint Co Ltd 塗膜の耐ハジキ性改良方法
JP2003213218A (ja) * 2001-11-15 2003-07-30 Kansai Paint Co Ltd 熱硬化性液状塗料組成物の塗膜平滑性改良方法
JP2005200506A (ja) * 2004-01-14 2005-07-28 Nippon Paint Co Ltd カチオン電着塗料組成物
JP2005200692A (ja) * 2004-01-14 2005-07-28 Nippon Paint Co Ltd カチオン電着塗膜の形成方法
WO2005068570A1 (fr) * 2004-01-14 2005-07-28 Nippon Paint Co., Ltd. Composition de revetement par electrodeposition cationique
JP2006257161A (ja) * 2005-03-15 2006-09-28 Nippon Paint Co Ltd カチオン電着塗料組成物、電着浴の管理方法および電着塗装システム

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