WO2016052661A1 - 低温走行環境での防錆性に優れる自動車用塗装金属板 - Google Patents
低温走行環境での防錆性に優れる自動車用塗装金属板 Download PDFInfo
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- WO2016052661A1 WO2016052661A1 PCT/JP2015/077845 JP2015077845W WO2016052661A1 WO 2016052661 A1 WO2016052661 A1 WO 2016052661A1 JP 2015077845 W JP2015077845 W JP 2015077845W WO 2016052661 A1 WO2016052661 A1 WO 2016052661A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B62—LAND VEHICLES FOR TRAVELLING OTHERWISE THAN ON RAILS
- B62D—MOTOR VEHICLES; TRAILERS
- B62D29/00—Superstructures, understructures, or sub-units thereof, characterised by the material thereof
- B62D29/001—Superstructures, understructures, or sub-units thereof, characterised by the material thereof characterised by combining metal and synthetic material
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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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
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
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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
- C09D5/08—Anti-corrosive paints
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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
- C09D5/08—Anti-corrosive paints
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
- C09D5/084—Inorganic compounds
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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
- C09D5/24—Electrically-conducting paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/48—Stabilisers against degradation by oxygen, light or heat
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
Definitions
- the present invention relates to a coated metal sheet for automobiles that has chipping resistance and is excellent in rust resistance in a low temperature driving environment.
- Most automobile body members are made of a metal plate such as a steel plate, and [1] a blanking process for cutting the metal plate into a predetermined size, [2] an oil washing process for washing the metal plate with oil, and [3] a blank. [4] a joining step for assembling the molded material into a member having a desired shape by spot welding or adhesion, [5] a step for degreasing and washing the press oil on the member surface, [6] a chemical conversion treatment step, [ 7] Manufactured through many processes called an electrodeposition coating process.
- the body member used as the outer plate is further subjected to a coating process such as [8] intermediate coating process and [9] top coating process. Therefore, in the automobile industry, there is a high need for cost reduction by omitting or simplifying the manufacturing process, particularly the chemical conversion treatment process and the painting process.
- a coated metal plate (pre-coated metal plate) is used for automobile body parts in order to eliminate the chemical conversion treatment process at the time of automobile manufacturing, to omit or simplify the electrodeposition coating process, and to eliminate or reduce the use of secondary materials.
- the use has been studied in the past.
- Chipping resistance refers to a phenomenon in which stones and the like that are thrown up when the automobile is traveling collide with the vehicle body, and at that time, the coating film and the plating film are destroyed and peeled off. This phenomenon is an important problem in cold regions and is called a low temperature chipping phenomenon. In a cold region, the coating film is exposed to a low temperature, and internal stress that tries to shrink is working. When an impact such as a stone jump is applied to the coating film, not only the coating film is damaged, but also the underlying plating film is damaged, and further, a crack may be generated at the interface between the plating film and the steel plate. This is considered to be because the internal stress of the coating film acts on the plating film. Such a peeled portion of the plating film immediately leads to a decrease in corrosion resistance, which is a major problem of the automobile body coating system.
- a chipping primer is inserted between the electrodeposition coating film and the intermediate coating film.
- the purpose of the chipping primer is to alleviate the impact on the coating film when a stone collides by functioning as a cushion layer. Therefore, the properties of the chipping primer are required to be high in the elasticity of the coating film, high in the elongation rate of the coating film and high in coating film strength.
- an aqueous chipping primer having a glass transition temperature (Tg) adjusted to 0 to ⁇ 75 ° C. is described in Patent Document 1 (Japanese Patent Laid-Open No. 2003-251272).
- Patent Document 2 Japanese Patent Laid-Open No. 2003-245605
- Patent Document 3 Japanese Patent Laid-Open No. 2005-155516
- rubber particles that absorb the impact of chipping are contained in the intermediate coating film to prevent chipping.
- a method for forming a laminated coating film that imparts properties and does not apply a chipping primer is described.
- Patent Document 4 Japanese Patent Application Laid-Open No. 2003-253211 discloses a water-based intermediate coating composition having a chipping resistance comprising a coating film-forming resin, a curing agent, a color pigment, talc and a silane coupling agent. ing.
- Patent Documents 2 to 4 are all for the purpose of omitting a chipping primer by imparting chipping resistance to an intermediate coating layer to be laminated after applying an undercoat paint such as an electrodeposition paint to an automobile steel plate. Yes. On the other hand, there is still no automobile body coating system in which a coated metal plate is used for a member for an automobile body, chipping resistance is imparted to the coating film itself of the coated metal plate, and a chipping primer is omitted.
- the present invention has been made in view of the above-described problems, and relates to a coated metal sheet for automobiles that has chipping resistance and is excellent in rust resistance in a low-temperature traveling environment.
- the inventors have a high elongation rate used in conventional chipping primers, and an organic resin having a glass transition temperature Tg of 0 ° C. or less is applied to the coating film of the coated metal plate to impart chipping resistance. It has been found that the chipping primer can be omitted.
- a coating film formed from an organic resin having a glass transition temperature Tg of 0 ° C. or lower has a problem that it has adhesiveness at room temperature, and the upper and lower coated metal plates stick together when stored in a laminated state. It was.
- the present inventors have solved this problem by including particles having a specific hardness in the coating film, and obtain a coated metal sheet for automobiles having chipping resistance according to the present invention. Was able to.
- a coated metal plate for automobiles comprising a metal plate, and a coating film ( ⁇ ) on at least one surface of the metal plate,
- the coating film ( ⁇ ) includes an organic resin (A), a conductive pigment (B), and a rust preventive pigment (C),
- the micro-Martens hardness at ⁇ 20 ° C. on the surface of the coating film ( ⁇ ) is HM 10 to 200 (mg / mm 2 ) when 100 points are measured, and the micro-Martens at 40 ° C. on the surface of the coating film ( ⁇ ).
- a painted metal sheet for automobiles having a hardness of HM200 to 200,000 (mg / mm 2 ) when the hardness is measured at 100 points.
- the organic resin (A) is selected from the group consisting of a polyester resin, a polyurethane resin, an acrylic resin, or a modified product thereof.
- the conductive pigment (B) is selected from at least one of boride, carbide, nitride, and silicide, and has an electrical resistivity at 25 ° C. of 0.1 ⁇ 10 ⁇ 6 to 185 ⁇ 10 ⁇ 6 ⁇ cm.
- the painted metal sheet for automobiles according to [1] which is oxide ceramic particles.
- the antirust pigment (C) is a compound capable of releasing silicate ion, phosphate ion, vanadate ion, tungstate ion or molybdate ion, and / or a metal element selected from the group consisting of Si, Ti, Al and Zr
- Martens hardness at 40 ° C. contains 200mg / mm 2 ⁇ 200000mg / mm 2 of granular particles (D) in the coating film, automotive coated metal plate according to [1].
- the coating metal plate for automobiles of the present invention has a chipping resistance
- the coating metal plate is provided with a chipping primer coating process after the coating metal plate is processed and molded into an automobile part. There is no need.
- the chipping resistance of this coating film is particularly effective in a low temperature environment of ⁇ 15 ° C. or less, and can provide a coated metal sheet for automobiles having excellent corrosion resistance.
- FIG. 1 represents a schematic cross-sectional view of a conventional automotive coating composition having a chipping primer.
- FIG. 2 is a schematic diagram of a coating film cross section when a flying object collides with a member for an automobile body and the surface of the metal plate is exposed.
- FIG. 3 shows that a flying object collides with an automobile body member using the painted metal plate for automobiles of the present invention, the metal plate is exposed, and then the rust preventive component eluted from the coating film ( ⁇ ) is exposed by getting wet with water.
- coat by reacting on the surface of the metal plate which did is represented.
- FIG. 1 represents a schematic cross-sectional view of a conventional automotive coating composition having a chipping primer.
- FIG. 2 is a schematic diagram of a coating film cross section when a flying object collides with a member for an automobile body and the surface of the metal plate is exposed.
- FIG. 3 shows that a flying
- FIG. 4 shows that a flying object collides with an automobile body member using a coated metal plate for automobiles whose physical properties of the coating film ( ⁇ ) do not conform to the scope of the present invention, and the internal stress of the coating film ( ⁇ ) is Due to its large size, the upper layer film, including the plating layer, is largely peeled off, and the surface of the metal plate is exposed to a large extent.
- the schematic diagram of the coating-film cross section when not fully covered is represented.
- FIG. 5 shows a schematic view of a cross section of a coated metal sheet for automobiles of the present invention when there is a ground treatment.
- FIG. 6 shows a schematic view of a cross section of a painted metal sheet for automobiles according to the present invention when there is no ground treatment.
- FIG. 7 is a schematic view showing a distribution state of particles (P) in a cross section of the automobile coated metal plate of the present invention.
- the painted metal plate for automobiles of the present invention is, for example, a metal plate with a plating film in which at least a part of the surface is coated with a specific conductive coating film.
- the metal plate may be coated on both sides of the metal plate with a conductive coating film, or may be coated on only one side, or even if part of the surface is coated, It may be coated.
- the part covered with the conductive coating of the metal plate has excellent resistance weldability and corrosion resistance.
- the constituent metal of the metal plate with a plating film that can be used for the painted metal plate of the present invention can include, for example, aluminum, titanium, zinc, copper, nickel, and steel.
- the components of these metals are not particularly limited.
- steel when steel is used, it may be ordinary steel or steel containing additive elements such as chromium.
- additive elements such as chromium.
- the metal plate of the present invention is press-molded, the type and amount of additive elements and the metal structure are appropriately controlled so as to have the desired formability followability in any metal plate. Is preferred.
- the type of the surface plating film is not particularly limited.
- Applicable plating films include, for example, plating containing any one of zinc, aluminum, cobalt, tin, and nickel, and alloy plating containing these metal elements, other metal elements, and nonmetal elements. Etc.
- a zinc-based plating film for example, plating made of zinc, alloy plating of zinc and at least one of aluminum, cobalt, tin, nickel, iron, chromium, titanium, magnesium, manganese, or other
- Various zinc-based alloy plating containing metal elements and non-metal elements for example, quaternary alloy plating of zinc, aluminum, magnesium, and silicon
- alloy components other than zinc are not particularly limited.
- these plating films contain small amounts of foreign metal elements or impurities such as cobalt, molybdenum, tungsten, nickel, titanium, chromium, aluminum, manganese, iron, magnesium, lead, bismuth, antimony, tin, copper, cadmium, arsenic. Etc. may be contained, and those in which inorganic substances such as silica, alumina, titania and the like are dispersed may be included.
- Examples of the aluminum-based plating film include plating made of aluminum, or alloy plating of at least one of aluminum and silicon, zinc, and magnesium (for example, alloy plating of aluminum and silicon, alloy plating of aluminum and zinc, aluminum, silicon, and magnesium). Ternary alloy plating) and the like.
- multi-layer plating in combination with the above-mentioned plating and other types of plating such as iron plating, iron-phosphorus alloy plating, nickel plating, cobalt plating and the like is also applicable.
- the method for forming the plating film is not particularly limited.
- electroplating, electroless plating, hot dipping, vapor deposition plating, dispersion plating, or the like can be used.
- the plating method may be either a continuous type or a batch type.
- post-plating treatments include zero spangle treatment, which is a uniform appearance after hot dipping, annealing treatment, which is a modification of the plating film, temper rolling for surface condition and material adjustment, etc.
- the present invention is not particularly limited to these, and any of them can be applied.
- the coating film ( ⁇ ) for coating the metal plate of the present invention contains an organic resin (A), a conductive pigment (B), and a rust preventive pigment (C), and is ⁇ 20 ° C. on the surface of the coating film ( ⁇ ).
- A organic resin
- B conductive pigment
- C a rust preventive pigment
- the point or more is HM200 to 200,000 (mg / mm 2 ).
- the micro Martens hardness HM is usually an index indicating hardness, but in the present invention, the hardness of the surface of the coating film ( ⁇ ) is defined.
- the micro Martens hardness HM can be measured by using a nanoindenter HM500 manufactured by Fischer Instruments and setting the indentation depth to 5 ⁇ m or less in a coating film having a thickness of 10 ⁇ m or more. For coatings with a thickness of less than 10 ⁇ m, it can be measured by setting the indentation depth to 1/5 of the coating thickness. In this case, since the dispersion of measurement increases, the number of measurements is increased as appropriate, and the average value is used as the measured value. To do.
- HM is 10 to 200 (at 20 points or more).
- mg / mm 2 in and, when measured at 100 points randomly micro Martens hardness HM at and 40 ° C., in the case of HM is from 200 to 200,000 with them five points or more (mg / mm 2), the present invention It was assumed that it was a painted metal plate for automobiles.
- HM minute Martens hardness HM at ⁇ 20 ° C.
- HM was 10 to 200 (mg / mm 2 ) at 40 points or more
- minute Martens hardness HM at 40 ° C. was randomized.
- 100 points of minute Martens hardness HM at ⁇ 20 ° C. are measured randomly
- the HM is 10 to 200 (mg / mm 2 ) at 60 points or more and the micro-Martens hardness HM at 40 ° C. is randomly measured at 100 points
- the HM is 200 to 200,000 (mg / mm at 20 or more points).
- mm 2 is more preferable.
- random means to eliminate arbitraryness that results in biased measurement results when selecting 100 measurement points. For example, two arbitrary points are set, and 100 points are selected at regular intervals or at random intervals between them, and the micro-Martens hardness HM at 20 ° C. and the micro-Martens hardness HM at 40 ° C. can be measured. In that case, it is desirable that the interval between adjacent measurement points be a position where the measurement points are not affected by the hardness of each other. In addition, although the number is 100, it is considered that as the number of measurement points increases, the measurement values are averaged and the accuracy is further improved.
- the coating film ( ⁇ ) of the present invention which has been subjected to electrodeposition coating, intermediate coating, and top coating for automobiles, is subjected to a stone jump that has come in a low temperature environment
- the coating film When ( ⁇ ) is sufficiently flexible even in a low temperature environment, it has been found that significant damage leading to the peeling of the plating layer due to the impact of hopping is suppressed as compared with the case where it is not. Further, it has been found that when the coating film ( ⁇ ) has a low Martens hardness in a low temperature range of 10 to 200 (mg / mm 2 ), significant scratches are suppressed.
- the coating film ( ⁇ ) When the coating film ( ⁇ ) is not sufficiently flexible at a low temperature, the top coating film, intermediate coating film, and electrodeposition coating film are destroyed by the impact of hopping, and in addition, the coating film ( ⁇ ) is destroyed. In this case, it was found that the shrinkage stress of these coating films released by breakage is transmitted as the stress that peels the plating layer, and as a result, the plating layer is largely peeled off.
- HM micro-Martens hardness measured from the surface of the coating film ( ⁇ ) is -20 ° C., 20 points or more per 100 random points, and 10 to 200
- the coating film ( ⁇ ) was flexible to the extent that the above effects were sufficiently exhibited.
- HM exceeded 200, the coating film ( ⁇ ) was not flexible, and the effect of suppressing the transfer of the shrinkage stress of the coating film to the plating layer was insufficient.
- the lower limit of HM at ⁇ 20 ° C. is not particularly defined, but a resin that realizes a coating film ( ⁇ ) of less than 10 cannot be obtained at ordinary industrial cost, so this value is substantially The lower limit.
- a low-temperature, flexible coating ( ⁇ ) having a part where the HM at ⁇ 20 is 200 or less is a range between 20 and 40 ° C. so-called room temperature storage and transportation, etc.
- the coating films ( ⁇ ) are adhered or fused to each other, and industrial handling tends to be hindered.
- the micro-Martens hardness HM measured from the surface of the coating film ( ⁇ ) is 200 to 200,000 at 40 ° C. and 5 or more per 100 measurement points at random, The mutual adhesion or fusion between the coating films ( ⁇ ) was sufficiently suppressed.
- the HM at 40 ° C is thus high on the surface of the coating ( ⁇ ). Presumed that the presence of the part suppresses the contact between the parts having a low HM of ⁇ 10 to 200 at ⁇ 20 ° C., and as a result, the adhesion or fusion between the coating films ( ⁇ ) is prevented. Is done. When the portion where the micro-Martens hardness HM is 200 to 200,000 at 40 ° C. is less than 5 points per 100 random measurement points, the above-described effect is lowered.
- the fine Martens hardness HM at ⁇ 20 ° C. of the coating film ( ⁇ ) can be generally controlled by appropriately selecting the organic resin (A) and the curing agent of the coating film composition.
- the resin molecular structure includes a flexible structure in which the molecular weight between cross-linking points is large and easily deformed, and the cross-linking density between resin molecular chains is kept low by adjusting the type and addition amount of the curing agent. It is possible to use a technique such as reducing the crosslinking reaction by the curing agent by reducing the baking temperature of the coating film and shortening the baking time.
- the coating composition for obtaining the coating film ( ⁇ ) in the present invention is referred to as a coating composition ( ⁇ ).
- examples of the coating composition ( ⁇ ) include a water-based coating composition and an organic solvent-based coating composition.
- the “water-based coating composition” refers to a composition formed using an “water-based solvent” in which water is 50% by mass or more of the entire solvent.
- the “organic solvent-based coating composition” refers to a composition formed using an “organic solvent-based solvent” in which the organic solvent is 50% by mass or more of the entire solvent.
- components other than water in the “aqueous solvent” include inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, boric acid, and hydrofluoric acid, which are well mixed with water, and metal salts and ammonium salts of the inorganic acids.
- inorganic salts such as those that dissolve in water, inorganic compounds such as silicates, thiosulfates, and thiocyanates that dissolve in water, and organic compounds that are miscible with water.
- an organic solvent can also be added to said "aqueous solvent” as needed.
- the “water-based coating composition” of the present invention uses organic solvents, etc.
- a method for forming a film on a metal plate for example, in the case of a water-based or solvent-based coating composition, known coating such as roll coating, groove roll coating, curtain flow coating, roller curtain coating, dipping (dip), air knife drawing, etc.
- a method for curing these dry coating films polymerization and curing by baking an organic resin in the coating film is preferable.
- the resin in the coating film can be polymerized with ultraviolet rays, polymerization or curing by ultraviolet irradiation is performed.
- the resin in the coating film can be polymerized with an electron beam, polymerization or curing by electron beam irradiation may be used.
- an undercoat film may be provided between the coating film and the metal plate surface.
- the number and composition of the layers are not limited, but the ground treatment film is formed on the metal plate so as not to impair the processing followability and corrosion resistance of the coating film ( ⁇ ) when forming the metal plate.
- the undercoat film has a chromate-free configuration.
- the thickness of the base treatment film be 0.5 ⁇ m or less.
- the method for forming the base treatment film is not limited as long as it is an industrially applicable film formation method.
- the method for forming the surface treatment film include methods such as coating, vapor deposition, and film sticking of the surface treatment composition. From the viewpoint of film formation cost (productivity) and versatility, an aqueous or solvent-based substrate is used. A method of coating and drying the treatment composition is preferred. When using a water-based or solvent-based surface treatment composition, a plurality of coating films including the surface treatment film are coated and dried repeatedly (sequential coating method) for each layer from the bottom layer to the top surface layer. A layer coating may be formed.
- the wet-on-wet coating method is a method in which a coating solution is applied onto a metal plate, and another coating solution is applied on the solvent-containing state (wet state) before the coating solution is dried.
- the solvent of the laminated coating solution obtained is simultaneously dried and cured to form a film.
- the multi-layer simultaneous coating method is a method in which multiple layers of coating liquid are applied simultaneously on a metal plate in a laminated state using a multilayer slide curtain coder, slot die coater, etc. It is a method to form a film.
- the average thickness of the coating film ( ⁇ ) covering the metal plate of the present invention is preferably in the range of 0.5 to 30 ⁇ m, more preferably in the range of 1 to 15 ⁇ m. If the thickness is less than 0.5 ⁇ m, the coating film is too thin to hold a sufficient amount of rust preventive pigment, and corrosion resistance may not be obtained. When the coating film thickness exceeds 30 ⁇ m, the amount of the coating composition ( ⁇ ) to be used increases, resulting in an increase in production cost, and the coating film may be cohesively broken or peeled off during press molding. In addition, since the film is thick, electrical insulation in the film thickness direction is increased, and resistance welding becomes difficult. Furthermore, when a water-based coating composition is used, there is a high possibility of occurrence of coating film defects such as armpits, and it is not easy to stably obtain the appearance necessary for industrial products.
- the thickness of the coating film ( ⁇ ) can be measured by observing the section of the coating film. Note that the mass of the coating film adhering to the unit area of the metal plate is calculated by dividing by the specific gravity of the coating film or the specific gravity after drying of the coating composition ( ⁇ ), but when measured by cross-sectional observation Since it should be the same measurement value, it can also be based on the method of calculating with specific gravity simply.
- the adhesion mass of the coating film is the mass difference before and after coating, the mass difference before and after peeling of the coating film after coating, or the presence of an element whose content in the coating film is known in advance by fluorescent X-ray analysis. It is possible to appropriately select from existing methods such as measuring the amount.
- the specific gravity of the coating film or the coating composition ( ⁇ ) after drying is determined by measuring the volume and mass of the isolated coating film after taking an appropriate amount of the coating composition ( ⁇ ) in a container and drying it. It can be appropriately selected from existing methods such as measuring the volume and mass, or calculating from the blending amount of the coating film components and the known specific gravity of each component.
- the organic resin (A) of the present invention is a binder component of the coating film ( ⁇ ), and by selecting it appropriately, the fine martens at ⁇ 20 ° C. required for the coating film of the automobile coated metal sheet of the present invention. Hardness HM and Tg can be obtained.
- the organic resin (A) may be either water-based or organic solvent-based resin, and is particularly the resin (A1) described later.
- the organic resin (A) can further contain a reaction derivative (A2) of the resin (A1).
- the organic resin (A) of the present invention is described in detail below, but preferably has a glass transition temperature Tg of ⁇ 80 ° C. to ⁇ 20 ° C.
- the coating composition ( ⁇ ) used for forming the coating film ( ⁇ ) in the present invention can be used in either an aqueous system or an organic solvent system, and the resin (A1) described later contains 50 to 100 mass of nonvolatile components. % Is included.
- the resin (A1) is stably present in the coating composition ( ⁇ ). When such a coating composition ( ⁇ ) is applied to a metal plate and heated, in many cases, the resin (A1) does not react and is dried as it is.
- at least a part of the resin (A1) contains a silane coupling agent, a curing agent, a crosslinking agent, etc. in the coating composition ( ⁇ ), it reacts with them to produce a derivative (A2) of the resin (A1) Form.
- the organic resin (A) that is a binder component of the coating film ( ⁇ ) includes the unreacted resin (A1) and the reaction derivative (A2) of the resin (A1).
- a polyurethane resin for example, a polyester resin, an epoxy resin, a (meth) acrylic resin, polyolefin Examples thereof include resins or modified products thereof.
- a polyurethane resin for example, a polyester resin, an epoxy resin, a (meth) acrylic resin, polyolefin Examples thereof include resins or modified products thereof.
- One or two or more of these may be mixed and used as the resin (A1), or one or more organic resins obtained by modifying at least one organic resin may be mixed and You may use as resin (A1).
- said resin (A1) it is preferable to use a polyurethane resin, a polyurethane resin modified body, a polyurethane resin composite, a mixture of these and other resins, and the like. Since the urethane group (—NHCOO—) in the polyurethane resin has higher molecular cohesive energy (8.74 kcal / mol) than many other organic groups, if the polyurethane resin is contained in the resin (A1), The adhesion of the coating film becomes high, and during press molding, peeling and galling of the coating film do not easily occur. In addition, the corrosion factor shielding (coating density) is improved by the relatively high cohesive energy, thereby improving the corrosion resistance. There is an effect to increase.
- Organic groups other than urethane groups such as methylene group (—CH 2 —), ether group (—O—), secondary amino group (imino group, —NH—), ester group (—COO—), benzene ring
- the molecular aggregation energy is 0.68 kcal / mol, 1.00 kcal / mol, 1.50 kcal / mol, 2.90 kcal / mol, 3.90 kcal / mol, respectively, and the molecular aggregation energy of the urethane group (—NHCOO—) is , Quite high compared to these.
- a coating film containing a polyurethane resin has higher adhesion and higher corrosion resistance than a coating film made of many other resins such as a polyester resin, a (meth) acrylic resin, and a polyolefin resin.
- the type of the resin (A1) is not particularly limited as long as it has a necessary glass transition temperature Tg.
- a carboxyl group (—COOH), a carboxylate group (—COO ⁇ M + , M + is a monovalent cation), a sulfonate group (—SO 3 H), a sulfonate group (—SO 3 ⁇ M + ;
- M + is a monovalent cation), primary amino group (—NH 2 ), secondary amino group (—NHR 1 ; R 1 is a hydrocarbon group), tertiary amino group (—NR 1 R 2 R 1 and R 2 are hydrocarbon groups), quaternary ammonium base (—N + R 1 R 2 R 3 X ⁇ ; R 1 , R 2 and R 3 are hydrocarbon groups, X ⁇ is a monovalent anion), Sulfonium base (—S + R 1 R 2 X ⁇ ; R 1 and R 2 are hydrocarbon groups,
- the resin used for the coating composition ( ⁇ ) for obtaining the coating film ( ⁇ ) includes water-soluble and solvent-soluble resins that are completely soluble in water and organic solvents, and emulsions and suspensions.
- (meth) acrylic resin means acrylic resin and methacrylic resin.
- examples of the polyurethane resin include those obtained by reacting a polyol compound with a polyisocyanate compound and then further chain-extending with a chain extender.
- the polyol compound is not particularly limited as long as it is a compound containing two or more hydroxyl groups per molecule.
- examples include glycols, glycerin, trimethylol ethane, trimethylol propane, polycarbonate polyols, polyester polyols, polyether polyols such as bisphenol hydroxypropyl ether, polyester amide polyols, acrylic polyols, polyurethane polyols, or mixtures thereof.
- the polyisocyanate compound is not particularly limited as long as it is a compound containing two or more isocyanate groups per molecule, and examples thereof include aliphatic isocyanates such as hexamethylene diisocyanate (HDI) and fats such as isophorone diisocyanate (IPDI).
- An aromatic diisocyanate such as cyclic diisocyanate, tolylene diisocyanate (TDI), an araliphatic diisocyanate such as diphenylmethane diisocyanate (MDI), or a mixture thereof.
- the chain extender is not particularly limited as long as it is a compound containing one or more active hydrogens in the molecule, and water or an amine compound can be applied.
- amine compounds include aliphatic polyamines such as ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, and tetraethylenepentamine, and aromatic polyamines such as tolylenediamine, xylylenediamine, and diaminodiphenylmethane.
- alicyclic polyamines such as diaminocyclohexylmethane, piperazine, 2,5-dimethylpiperazine, and isophoronediamine; hydrazines such as hydrazine, succinic dihydrazide, adipic dihydrazide, and phthalic dihydrazide; and hydroxyethyldiethylenetriamine, 2- And alkanolamines such as [(2-aminoethyl) amino] ethanol and 3-aminopropanediol.
- an aqueous polyurethane resin for example, at the time of resin production, at least a part of the polyol compound is replaced with a carboxyl group-containing polyol compound, reacted with a polyisocyanate compound to introduce a carboxyl group into the resin chain, Can be neutralized with a base to form a water-based resin.
- at the time of resin production at least a part of the polyol compound is replaced with a polyol compound having a secondary amino group or a tertiary amino group in the molecule and reacted with a polyisocyanate compound to form a secondary amino group or tertiary on the resin chain.
- water-based resin examples include neutralization with an acid after introduction of an amino group.
- the resin chain has a tertiary amino group, it can be made quaternized by introducing an alkyl group into the tertiary amino group to be an aqueous cationic resin having a quaternary ammonium base.
- These compounds can be used alone or in a mixture of two or more.
- the polyurethane resin that can be used as the resin (A1) it is preferable to use a polyurethane resin containing a large number of aromatic rings in the molecular structure.
- Such polyurethane resins have a higher glass transition temperature, a rigid molecular chain, a higher resistance to deformation of the coating film, and a longer elongation of the coating film than polyurethane resins having no or few aromatic rings in the molecular structure. Since the deformation rate is low, the hardness and brittleness of the coating film ( ⁇ ) required in the present invention are high compared to a polyurethane resin having no aromatic rings or few aromatic rings.
- the polyol compound, polyisocyanate compound, and chain extender used for resin production are not particularly limited, but it is preferable to use an araliphatic or araliphatic compound containing a large amount of aromatic rings.
- the polyester resin is not particularly limited as long as it has the necessary HM and glass transition temperature Tg.
- Tg glass transition temperature
- the epoxy resin is not particularly limited as long as it has the necessary HM and glass transition temperature Tg.
- bisphenol A type epoxy resin, bisphenol F type epoxy resin, resorcin type epoxy resin, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, resorcin type epoxy resin, novolac type epoxy resin, etc. It can be obtained by reacting with an amine compound such as N-methylethanolamine. Furthermore, these are neutralized with an organic acid or inorganic acid to form an aqueous resin, or after radical polymerization of a high acid value acrylic resin in the presence of the epoxy resin, neutralized with ammonia or an amine compound to make an aqueous system. Can be mentioned.
- the (meth) acrylic resin is not particularly limited as long as it has the necessary HM and glass transition temperature Tg.
- examples thereof include those obtained by radical polymerization of (meth) acrylates such as (meth) acrylates with (meth) acrylic acid in water using a polymerization initiator.
- the polymerization initiator is not particularly limited, and for example, persulfates such as potassium persulfate and ammonium persulfate, azo compounds such as azobiscyanovaleric acid and azobisisobutyronitrile can be used.
- persulfates such as potassium persulfate and ammonium persulfate
- azo compounds such as azobiscyanovaleric acid and azobisisobutyronitrile
- (meth) acrylate” means acrylate and methacrylate
- (meth) acrylic acid” means acrylic acid and methacrylic acid.
- the polyolefin resin is not particularly limited as long as it has a necessary glass transition temperature Tg.
- examples thereof include radical polymerization of ethylene and unsaturated carboxylic acids such as methacrylic acid, acrylic acid, maleic acid, fumaric acid, itaconic acid and crotonic acid under high temperature and high pressure. Further, these can be further neutralized with ammonia, amine compounds, basic metal compounds such as KOH, NaOH, LiOH, or ammonia or amine compounds containing the above metal compounds to obtain water-based resins.
- the resin (A1) may be used alone or in combination of two or more. Further, as a main component of the coating composition ( ⁇ ), one or more composite resins obtained by modifying at least part of the resin (A1) in the presence of at least one resin (A1) or Two or more kinds may be collectively used as the resin (A1).
- the glass transition temperature Tg of the organic resin (A) is preferably ⁇ 80 ° C. to ⁇ 20 ° C.
- the glass transition temperature Tg is obtained by heating and curing the organic resin forming the coating film at an ultimate temperature of 200 ° C. to form a film having a film thickness of 15 ⁇ m, and measuring the peak temperature or dynamic viscoelasticity of a differential scanning calorimeter (DSC). It can be measured as the transition temperature in the machine.
- Tg is preferably from ⁇ 80 ° C. to ⁇ 20 ° C. Resins having a Tg higher than ⁇ 20 ° C.
- Tg is not particularly defined, but organic resins having a low Tg exceeding -80 ° C. are difficult to obtain industrially at low cost. Furthermore, Tg is preferably ⁇ 60 ° C. or higher and ⁇ 30 ° C. or lower.
- conductive pigment (B) As the conductive pigment (B), it is preferable to use one or more selected from metals, alloys, conductive carbon, iron phosphide, carbides, and semiconductor oxides.
- metals such as zinc, nickel, iron, aluminum, cobalt, manganese, copper, tin, chromium or their alloy powder, conductive carbon powder such as conductive carbon and graphite powder, iron phosphide powder, titanium carbide, carbonized
- carbide powder such as silicon, conductive semiconductor powder, and ceramic particles.
- non-oxide ceramic particles are particularly preferable in the coated metal plate of the present invention.
- non-oxide ceramic particles when used, even when the coating composition ( ⁇ ) for obtaining the coating film ( ⁇ ) is an aqueous composition, these non-oxide ceramic particles do not deteriorate in the composition, High conductivity is permanently retained. Therefore, superior resistance weldability can be maintained for a very long period of time compared to conductive particles that deteriorate due to moisture, such as base metal particles and ferrosilicon particles.
- the non-oxide ceramic constituting the non-oxide ceramic particles contained in the coating film ( ⁇ ) of the present invention has an electrical resistivity (volume resistivity, specific resistance) at 25 ° C. of 0.1 ⁇ 10 ⁇ 6 to 185 ⁇ .
- the non-oxide ceramic referred to here is a ceramic made of an element or compound not containing oxygen.
- the boride ceramics, carbide ceramics, nitride ceramics, and silicide ceramics referred to here are non-oxide ceramics containing boron B, carbon C, nitrogen N, and silicon Si as the main non-metallic constituent elements, respectively. It is.
- the non-oxide ceramic particles contained in the coating film ( ⁇ ) of the present invention have high conductivity, a smaller amount may be added for imparting sufficient conductivity to the resin coating film. The adverse effect on the corrosion resistance and formability of the metal plate is reduced.
- the electrical resistivity of a pure metal is in the range of 1.6 ⁇ 10 ⁇ 6 ⁇ cm (Ag simple substance) to 185 ⁇ 10 ⁇ 6 ⁇ cm (Mn simple substance), and is used as a conductive particle in the present invention. It can be seen that oxide ceramics (electrical resistivity 0.1 ⁇ 10 ⁇ 6 to 185 ⁇ 10 ⁇ 6 ⁇ cm) have excellent conductivity equivalent to that of pure metal.
- non-oxide ceramics examples include the following. That is, as boride ceramics, transition metal of group IV (Ti, Zr, Hf), group V (V, Nb, Ta), group VI (Cr, Mo, W) of the periodic table, Mn, Fe, Examples thereof include borides of alkaline earth metals (Ca, Sr, Ba) other than Co, Ni, rare earth elements, or Be, Mg.
- Be borides whose electrical resistivity at 25 ° C. exceeds 185 ⁇ 10 ⁇ 6 ⁇ cm are not sufficiently conductive, and thus are applicable to the present invention. Not suitable for. Also, Mg borides (Mg 3 B 2 , MgB 2, etc.) are not suitable for application to the present invention because they are unstable to water and acids.
- carbide ceramics include Group IV, Group V, Group VI transition metals, and carbides of Mn, Fe, Co, and Ni.
- carbides of rare earth elements or alkaline earth metals that may be hydrolyzed in a humid atmosphere for example, YC 2 , LaC 2 , CeC 2 , PrC 2 , Be 2 C, Mg 2 C 3 , SrC 2, etc. Is not suitable for application to the present invention.
- nitride ceramics include group IV, group V, and group VI transition metals, or nitrides of Mn, Fe, Co, and Ni.
- rare earth elements and alkaline earth metal nitrides for example, LaN, Mg 3 N 2 , Ca 3 N 2, etc.
- silicide ceramics include Group IV, Group V, and Group VI transition metals, or silicides of Mn, Fe, Co, and Ni.
- silicides of rare earth elements or alkaline earth metals for example, LaSi, Mg 2 Si, SrSi 2 , BaSi 2, etc.
- silicides of rare earth elements or alkaline earth metals that may generate hydrogen by reacting with water in a humid atmosphere are not included in the present invention. Not suitable for application.
- a mixture of two or more selected from these borides, carbides, nitrides and silicides, or cermets obtained by mixing these ceramics with a metal binder and sintering them can be exemplified.
- the standard electrode potential of the metal constituting a part of the cermet is ⁇ 0.3 V or more and is water-resistant.
- the standard electrode potential of the metal constituting a part of the cermet is less than ⁇ 0.3 V, if this cermet particle is present in the aqueous coating composition for a long time, a rust layer or a thick oxide insulating layer is formed on the surface of the particle. This is because the conductivity of the particles may be lost.
- water-resistant cermet particles include WC-12Co, WC-12Ni, TiC-20TiN-15WC-10Mo 2 C-5Ni, and the like.
- the standard electrode potentials of Co and Ni are ⁇ 0.28 V and ⁇ 0.25 V, respectively, which are nobler than ⁇ 0.3 V, and both metals are resistant to water.
- non-oxide ceramics Of the non-oxide ceramics described above, Cr-based ceramics (CrB, CrB 2 , Cr 3 C 2 , Cr 2 N, CrSi, etc.) are concerned with environmental load, and Hf-based ceramics (HfB 2 , HfC, HfN). Etc.), since many of rare earth element-based ceramics on the side of rare earth than Tb are expensive and are not distributed in the market, in the present invention, non-oxide ceramics excluding these from the above group, Alternatively, it is preferable to use a mixture of two or more selected from these.
- non-oxide ceramics are more preferable from the viewpoints of the presence or absence of industrial products, stable distribution in domestic and overseas markets, price, electrical resistivity, and the like. That is, BaB 6 (electric resistivity 77 ⁇ 10 ⁇ 6 ⁇ cm), CeB 6 (30 ⁇ 10 ⁇ 6 ⁇ cm), Co 2 B (33 ⁇ 10 ⁇ 6 ⁇ cm), CoB (76 ⁇ 10 ⁇ 6 ⁇ cm).
- non-oxide ceramics having an electrical resistivity at 25 ° C. of 0.1 ⁇ 10 ⁇ 6 to 100 ⁇ 10 ⁇ 6 ⁇ cm are particularly preferable. Because they have higher electrical conductivity than non-oxide ceramics whose electrical resistivity at 25 ° C. is in the range of more than 100 ⁇ 10 ⁇ 6 ⁇ cm and up to 185 ⁇ 10 ⁇ 6 ⁇ cm, it is sufficient for resin coatings. This is because the amount of particles added for imparting electrical conductivity may be smaller, and only a small number of corrosion current conduction paths penetrating the coating film are formed, and the corrosion resistance is hardly lowered. In addition, since the addition of particles is small, the moldability hardly deteriorates without inducing peeling or galling of the coating film during press molding.
- the electrical resistivity indicated in parentheses of the non-oxide ceramic is a representative value (literature value) of what is sold and used as an industrial material. Since these electrical resistivity increases and decreases depending on the type and amount of impurity elements that have entered the crystal lattice of the non-oxide ceramics, when used in the present invention, for example, a resistivity meter manufactured by Mitsubishi Chemical Analytech Co., Ltd.
- the conductive pigment (B) has a particle shape of spherical particles, pseudo-spherical particles (for example, elliptical sphere shape, egg shape, rugby ball shape, etc.) or polyhedral particles (for example, soccer ball shape, dice shape, brilliant of various jewels).
- Slender shapes eg, rods, needles, fibers, etc.
- flat shapes eg, flakes, flat plates, flakes, etc.
- the average particle diameter of the conductive pigment (B) is not particularly limited, but is preferably present as particles having a volume average diameter of 0.2 to 20 ⁇ m in the coating composition ( ⁇ ) of the present invention. It is more preferable that the particles have an average diameter of 0.5 to 12 ⁇ m, and it is particularly preferable that the particles have a volume average diameter of 1 to 8 ⁇ m.
- Dispersed particles with these volume average diameters are used in the coating composition ( ⁇ ) manufacturing process, storage and transport, and as a base material for coating, a metal plate (if the metal surface has a ground treatment, a ground treatment layer) As long as it is stably present in the coating composition ( ⁇ ) in the coating step or the like, it may be a single particle or a secondary particle in which a plurality of single particles are strongly aggregated.
- the (B) particles may be aggregated during the drying and film formation of the coating film, and the volume average diameter in the coating film may increase.
- the volume average diameter referred to here is the volume-based average diameter obtained from the volume distribution data of the particles. This may be determined using any generally known particle size distribution measurement method, but it is preferable to use the average value of the sphere volume equivalent diameter distribution measured by the Coulter method (pore electrical resistance method). preferable. This is because the Coulter method uses other particle size distribution measurement methods (for example, (a) Calculate from the volume distribution obtained by the laser diffraction scattering method, (b) The circular area equivalent diameter distribution obtained by the image analysis method is the volume distribution. Compared to (c) calculated from mass distribution obtained by centrifugal sedimentation method, etc.), there is almost no difference in measured values by measuring machine manufacturers and models, and accurate and highly accurate measurement can be performed.
- the test particles are suspended in an aqueous electrolyte solution, a constant current is passed through the pores of the glass tube, and the particles are set to pass through the pores by negative pressure.
- Non-oxide ceramic particles having a volume average diameter of less than 0.2 ⁇ m are generally more expensive than non-oxide ceramic particles having a volume average diameter larger than that, and few are marketed as industrial products.
- the specific surface area is relatively large, it is difficult to wet and disperse the entire particle surface using a wetting and dispersing agent when preparing a water-based or organic solvent-based coating composition. It is better not to use it in the present invention, because there are many cases where no splints or lumps occur.
- non-oxide ceramic particles having a volume average diameter exceeding 20 ⁇ m are more likely to settle faster in water-based or organic solvent-based coating compositions than non-oxide ceramic particles having a volume average diameter smaller than that (Stokes' formula).
- the available conductive pigment (B) is generally prepared to a predetermined particle size by pulverizing the raw material and classifying as necessary, so that the particle size in which particles having different particle sizes are mixed is used. Have a distribution. Therefore, even if the volume average diameter is in the above-mentioned particle size range, the weldability is affected depending on the particle size distribution.
- (B1) having a volume particle diameter of 0.25 to 24 ⁇ m has an effect particularly on good weldability.
- the content of the conductive pigment (B) in the coating film ( ⁇ ) at 25 ° C. is preferably 0.5 to 65% by volume, and the electrical conductivity during resistance welding, ensuring the formability, and the conductive pigment. From the viewpoint of an increase in cost due to the increase, it is more preferably 1 to 40% by volume, and further preferably 2 to 20% by volume. From the viewpoint of securing sufficient resistance weldability in addition to ensuring sufficient corrosion resistance and formability, the range of 4 to 20% by volume is particularly preferable.
- the reason why the coating film ( ⁇ ) exhibits good conductivity is that the conductive pigment (B) which is conductive particles hardly aggregates in the coating film ( ⁇ ), It is considered that it is sufficiently uniformly dispersed over the entire surface of the coating film, and the electrical conduction path to the underlying metal plate is not unevenly distributed in the coating film.
- the conductive particles are agglomerated in the coating film, an electric conduction path in a state of being uniformly dispersed over the entire coating surface is difficult to be formed in the coating film, and there is no electric conduction path in the coating film. There is a tendency to create areas that hinder resistance welding. In such a case, more conductive material must be added in order to secure a conduction path, and the possibility that good corrosion resistance and moldability cannot be maintained increases. In the coated metal plate of the present invention, such a problem is very unlikely to occur.
- the content of the conductive pigment (B) in the coating film ( ⁇ ) exceeds 65% by volume, sufficient conductivity can be maintained, but coating film peeling or galling is likely to occur during press molding, and good moldability. May not be retained, and the corrosion resistance of the film peeling site may be reduced. Moreover, when it exceeds 65 volume%, although the improvement effect of weldability will be saturated, the cost of electroconductive particle will become high.
- the addition of conductive particles of 0.5 vol% or more and less than 1 vol% of the coating film may result in insufficient electrical conductivity during resistance welding, and more than 40 vol% of the coating film,
- the moldability and cost compatibility may be insufficient, so the volume ratio of the conductive pigment (B) may be 1% by volume or more and less than 40% by volume. More preferred.
- the electrical conductivity during resistance welding may be slightly insufficient.
- the moldability and the cost compatibility may be slightly insufficient.
- addition of 2% by volume or more and less than 20% by volume is more preferable.
- 2% by volume or more and less than 4% by volume of conductive particles are added to the coating film, if resistance welding conditions are greatly changed, there is a risk that high and stable weldability cannot always be secured.
- Addition of less than volume% is particularly preferred.
- the content of the conductive pigment (B) in the coating film ( ⁇ ) is less than 0.5% by volume, good conductivity cannot be ensured because the amount of non-oxide ceramic particles dispersed in the coating film is small. Depending on the thickness of the coating film ( ⁇ ), sufficient resistance weldability may not be imparted to the coating film.
- Anti-rust pigment (C) Although it does not specifically limit as a kind of rust preventive pigment (C) used for this invention, It contains 1 type, or 2 or more types chosen from a silicate compound, a phosphate compound, a vanadate compound, and metal oxide fine particles. preferable.
- the silicate compound, phosphate compound, and vanadate compound are used in the coating composition ( ⁇ ) and the coating film ( ⁇ ), the moisture in the composition and the coating film, contact with coexisting substances and the substrate surface, Depending on environmental changes such as pH, silicate ions, phosphate ions, vanadate ions, and counter cations of these anions (eg, alkaline earth metal ions, Zn ions, Al ions, etc.) can be released, respectively. .
- the ions that have already eluted in the coating composition ( ⁇ ) are taken into the coating film ( ⁇ ) during film formation, and the increase or decrease of moisture in the coating film, the coexisting substances and the substrate surface It is considered that, depending on the contact with the substrate, pH change, etc., it forms a film of a hardly soluble salt or oxide with other coexisting atoms or atomic groups to suppress corrosion.
- a silicate compound, a phosphate compound, and a vanadate compound incorporated in the coating film ( ⁇ ) the anion and cation are gradually released according to the environmental change after the coating film is formed. It is thought to form a film of sparingly soluble salt or oxide to suppress corrosion.
- the above-mentioned action also releases silicate ions, phosphate ions, vanadate ions, and counter cations of these anions even when the coating film is scratched and the plating film on the metal plate or the underlying metal under plating is exposed. It is exhibited by reaching the exposed plating film or the surface of the underlying metal. This effect is more effectively exhibited when the degree of scratches is suppressed to be small and the exposed area of the plating film or base metal is limited to a small size.
- silicate compound examples include alkaline earth metal silicates such as magnesium silicate and calcium silicate, alkali metal silicates such as lithium silicate, sodium silicate, and potassium silicate, and aluminum silicate.
- alkaline earth metal silicates such as magnesium silicate and calcium silicate
- alkali metal silicates such as lithium silicate, sodium silicate, and potassium silicate
- aluminum silicate can be mentioned.
- lithium silicate, sodium silicate, and potassium silicate the constituent molar ratio of silicon oxide (SiO 2 ) and lithium oxide (Li 2 O) is 0.5 ⁇ (SiO 2 / Li 2 O) ⁇ 8.
- lithium orthosilicate Li 4 SiO 4 ; 2Li 2 O ⁇ SiO 2
- ortholithium hexalithium Li 6 Si 2 O 7 ; 3Li 2 O ⁇ 2SiO 2
- lithium metasilicate Li 2 SiO 3; Li 2 O ⁇ SiO 2)
- lithium disilicate Li 2 Si 2 O 5; Li 2 O ⁇ 2SiO 2
- seven silicate four lithium (2Li 2 O ⁇ 7SiO 2) seven silicate four lithium (2Li 2 O ⁇ 7SiO 2)
- four lithium silicate Li 2 Si 4 O 9; Li 2 O ⁇ 4SiO 2)
- nine silicate four lithium (2Li 2 O ⁇ 9SiO 2) fifteen silicate four lithium (2Li 2 O ⁇ 15SiO 2)
- sodium orthosilicate Na 4 SiO 4 ; 2Na 2 O ⁇ SiO 2)
- sodium metasilicate Na 2 SiO 3; Na 2 O ⁇ SiO 2
- sodium disilicate Na 2 Si 2 O 5; Na 2
- Examples of the phosphate compound that can be used in the present invention include orthophosphoric acid, polyphosphoric acid (a linear polymer having a degree of polymerization of orthophosphoric acid up to 6 or a mixture of two or more thereof), metaphosphoric acid ( Orthophosphoric acid cyclic polymer having a degree of polymerization of 3 to 6 or a mixture of two or more thereof, metal salts such as tetrametaphosphoric acid and hexametaphosphoric acid, phosphorous pentoxide, monetite, torphyllite, witrockite, xenotime , Phosphate minerals such as starcolite, struvite, orbite ore, commercially available complex phosphate pigments such as polyphosphate silica and tripolyphosphate, phytic acid, phosphonic acid (phosphorous acid), phosphinic acid (hypophosphorous acid) Or a metal salt thereof, or a mixture of two or more thereof.
- orthophosphoric acid polyphosphoric acid (a linear poly
- the orthophosphate referred to here includes its monohydrogen salt (HPO 4 2 ⁇ ) and dihydrogen salt (H 2 PO 4 ⁇ ).
- the polyphosphate includes a hydrogen salt.
- the cationic species that form the phosphate such as Co, Cu, Fe, Mn, Nb, Ni, Sn, Ti, V, Y, Zr, Al, Ba, Ca, Mg, Sr, and Zn.
- Metal ions, vanadyl, titanyl, zirconyl, and other oxo cations, and Al, Ca, Mg, Mn, and Ni are preferably used.
- the said phosphate compound may be used independently and may use 2 or more types together.
- alkali metal phosphate it is not preferable to use a large amount of alkali metal as the cationic species forming phosphate.
- the product obtained by firing in an industrial production process tends to be excessively dissolved in water.
- the solubility in water can be controlled by using anti-rust pigments, coating compositions, coatings on metal plates, or using painted metal plates. If it can be carried out at times, it may be used slightly more. Such control can be achieved by, for example, coexisting rust preventive pigments with other additives that suppress water solubility, or coexisting with highly crosslinked resin-based or inorganic polymers. Examples include a method of controlling the elution rate.
- the vanadate compound that can be used in the present invention is a composite compound in which the valence of vanadium is any one of 0, 2, 3, 4, or 5, or two or more kinds, These oxides, hydroxides, oxyacid salts of various metals, vanadyl compounds, halides, sulfates, metal powders, and the like. These decompose when heated or in the presence of water and react with the coexisting oxygen.
- a vanadium metal powder or a divalent compound finally changes to a trivalent, tetravalent, or pentavalent compound.
- Zero-valent ones, such as vanadium metal powder can be used for the above reasons, but are not preferred in practice because of problems such as insufficient oxidation reaction.
- vanadium compounds include vanadium (II) compounds such as vanadium oxide (II) and vanadium hydroxide (II), vanadium (III) compounds such as vanadium oxide (III), vanadium oxide (IV), and vanadyl halide.
- Vanadium (IV) compounds such as vanadium (IV) compounds, vanadium oxide (V), vanadate (ortho vanadates of various metals, metavanadate, pyrovanadate, etc.), etc., or a mixture thereof Can be mentioned.
- the preferred metal species constituting the vanadate are the same as the metals shown for the phosphate.
- alkali metal vanadate When alkali metal vanadate is used, the product obtained by calcination in an industrial manufacturing process tends to dissolve too much in water. Large amounts are not preferred. However, as long as the solubility in water can be controlled as in the case of using an alkali metal phosphate, these can be used. The same applies to vanadium halides and sulfates.
- the total amount of the silicate compound, phosphate compound, and vanadate compound is 1 to 40% by volume, preferably 1 to 20% by volume of the coating film ( ⁇ ). 2 to 15% by volume is more preferable. If it is less than 1% by volume, the silicate compound, the phosphate compound, and the vanadate compound are insufficient in action, and the corrosion resistance may be lowered. If it exceeds 20% by volume, the coating film becomes brittle, and the coating film adhesion and coating followability at the time of molding may decrease due to coating film cohesive failure, or the weldability may decrease.
- the rust preventive pigment (C) preferably contains one or more of silicate compounds, phosphate compounds, and vanadate compounds.
- the phosphate compound (phosphate ion source) and the silicate compound (silicic acid) It is more preferable that at least one kind of ion source) or vanadate compound (vanadate ion source) coexists in order to enhance the rust prevention effect.
- the ratio of the phosphate ion source and the total amount of the silicate ion source and vanadate ion source to be blended is the ratio of [number of moles of P 2 O 5 ]: [total number of moles of SiO 2 and V 2 O 5 ]: 25 More preferably, it is 75 to 99: 1.
- the rust preventive effect due to the phosphate ions may be reduced.
- the molar ratio of the total amount of the source and vanadate ion source is less than 1%, the effect of oxidizing and fixing peripheral chemical species by silicate ions (or vanadate ions) may be insufficient.
- the anticorrosive pigment (C) used in the present invention fine metal oxide particles composed of one or more metal elements selected from the group consisting of Si, Ti, Al and Zr can be used. Corrosion resistance can be further improved by using these metal oxide fine particles alone or by blending them together with a silicate compound, a phosphate compound and a vanadate compound. It is preferable that a silicate compound, a phosphate compound, a vanadate compound and silica coexist because the corrosion resistance is further improved.
- Examples of silica include fumed silica, colloidal silica, and agglomerated silica. Calcium deposited silica can also be used.
- metal oxide fine particles examples include silica fine particles having a volume average diameter of about 0.2 to 10 ⁇ m, alumina fine particles, titania fine particles, zirconia fine particles, and the like.
- Metal oxide nanoparticles having a size of about 0.5 to 30 nm are more preferable. These may be used alone or in combination of two or more. Among these, silica nanoparticles can be added when both improvement in corrosion resistance and toughening of the coating film are required.
- the metal oxide nanoparticle having a particle size of 0.5 nm or more and less than 30 nm for example, colloidal silica, colloidal titania, colloidal zirconia can be used. Since these are different in production method from those obtained by pulverizing the above metal oxide, the fine primary particle diameter (0.5 nm to 30 nm) remains in the paint and in the coating film of the painted metal material after painting. Easy to disperse. These metal oxide nanoparticles have a higher antirust effect than metal oxide particles having the same composition and a larger particle size. However, such metal oxide nanoparticles may impair weldability in current resistance welding, such as spot welding, in which current is applied while applying a load with an electrode and welding is performed by Joule heat.
- current resistance welding such as spot welding
- the amount of metal oxide nanoparticles is such that the ratio of the total volume of metal oxide nanoparticles in the coating film to the total volume of non-oxidized ceramic particles (B) (metal oxide nanoparticles / B) is 20 or less. It is preferable. When emphasizing the weldability, 10 or less is more preferable.
- the lower limit of (metal oxide nanoparticle / B) is preferably 0.1 or more. When (metal oxide nanoparticle / B) is less than 0.1, there are too many non-oxidized ceramic particles (B) in the coating film or too few metal oxide nanoparticles.
- the coating film becomes brittle, and coating film cracking or coating film dropping during molding may occur.
- a crack in the coating film or a drop in the coating film leads to a decrease in corrosion resistance due to the coating film or a poor appearance of the coated metal plate.
- the amount of the metal oxide nanoparticles in the coating film is insufficient, the effect of improving the corrosion resistance may not be sufficiently obtained.
- the antirust property which is lowered by suppressing the amount of the metal oxide nanoparticle in order to ensure the weldability can be supplemented by adding an antirust pigment (C) having a particle size of 100 nm or more.
- the anticorrosive pigment (C) having a particle size of 100 nm or more is formed between the electrode and (B) and (B) in a state where the coating film is applied on the metal plate or in a state where the coating film is deformed by a load by the welding electrode. Or, since it is difficult to enter between (B) and the metal plate, the adverse effect on current resistance welding is small compared to metal oxide nanoparticles.
- the amount of the rust preventive pigment (C) is preferably 1 to 40% by volume of the coating film ( ⁇ ), and the total amount with the amount of the conductive pigment (B) preferably does not exceed 80% by volume.
- the amount of the anticorrosive pigment (C) is preferably 3 to 40% by volume, more preferably 7.5 to 40% by volume.
- the amount of the rust preventive pigment (C) is more preferably 13 to 40% by volume. If the amount is less than 1% by volume, the amount of the anticorrosive pigment (C) is insufficient, and thus the effect of enhancing the corrosion resistance may not be sufficiently obtained. If it exceeds 40% by volume, the coating plate will be embrittled or the adhesion of the coating to the metal plate will be reduced. The effect of improving the corrosion resistance by the coating film may be reduced.
- the amount of the conductive pigment (B) and the amount of the anticorrosive pigment (C) are determined by observing the cross section of the coating film with an electron microscope and identifying each particle, counting the number per section, It can be calculated after conversion. In this case, each particle can be identified using an EDX spectroscopic device or the like as necessary. It is also possible to calculate the amount of each particle in the coating film from the amounts of (B) and (C) contained in the coating material before painting and the coating film adhesion amount to the metal plate. If the charged amounts of (B) and (C) in the paint before painting are known, the amount of each particle in the coating film can be calculated from the charged amount and the amount of paint adhered to the metal plate.
- the amount charged is unknown, for example, it can be calculated by identifying and counting the particles in the paint diluted to an appropriate concentration by image analysis using a device such as Malvern's particle image analyzer Morphologi G3. It is. This technique can also be used when the number of particles is counted by dissolving the coating film adhering to the metal plate.
- the amount of the conductive pigment (B) and the amount of the rust preventive pigment (C) in the coating film ( ⁇ ) are the mixing ratio of the organic resin (A), the conductive pigment (B) and the rust preventive pigment (C). Even if it is calculated based on each specific gravity after drying, it should be the same measurement value as that measured by observing the cross section, so that it can be simply calculated from the blending ratio.
- an appropriate amount of the various antirust pigments is previously dissolved or dispersed and stabilized in the coating composition ( ⁇ ) and then introduced into the organic resin (A) in the coating film ( ⁇ ).
- ⁇ Particle (D)> The conductive pigments (B), in addition to the rust-preventive pigment (C), as the particles in the coating film of the present invention, the Martens hardness of the granular 200mg / mm 2 ⁇ 200000mg / mm 2 at 40 ° C., the wax or resin Particles (D) such as beads may be included. Martens hardness at 40 ° C. particulate wax or resin beads 200mg / mm 2 ⁇ 200000mg / mm 2 can be arbitrarily selected in consideration of ease of addition to the coating material.
- polyolefin wax, polyethylene wax, polypropylene wax, polybutylene wax, modified polyolefin wax, acrylic resin particles, silicone resin particles, fluorine resin particles, polyacrylonitrile resin, and the like can be used.
- the resin (A) is used when the surfaces of the coated metal plates of the present invention are in contact with each other or with other materials, instruments, or tools. Are also preferentially contacted, and the effect of preventing the coating film ( ⁇ ) from sticking or melting is small. Particles (D) whose Martens hardness at 40 ° C. exceeds 200,000 mg / mm 2 are difficult to find industrially easily, and are substantially the upper limit of HM. Furthermore, the hardness range of the Martens hardness is more preferably in the range of 300 mg / m 2 to 2000 mg / m 2 .
- Particles selected from the above conductive pigment (B), rust preventive pigment (C), and particles (D) and having a primary particle diameter of 1 ⁇ m to 10 ⁇ m are defined as particles (P).
- the particles (P) are composed of at least one of a conductive pigment (B) and a rust preventive pigment (C), and may contain particles (D) as necessary.
- the exposed state of the particles (P) and the particle diameter thereof can be confirmed from above the painted metal plate or by observing the cross section with a microscope.
- the density of the exposed particles (P) can also be confirmed by observation from above the coated metal plate.
- the particle diameter and the number of particles of the raw material of the particles (P) are known, they may be calculated from the blending amount in the paint.
- the particles (P) exposed on the surface of the coating film ( ⁇ ) have a micro-Martens hardness HM at 40 ° C. of 200 to 200,000 (mg / mm 2 ) and constitute at least a part of the surface of the coating film ( ⁇ ).
- the particles (P) exposed on the surface of the coating film ( ⁇ ) are less likely to be deformed than the resin (A) constituting the coating film ( ⁇ ).
- they When contacting the surfaces of each other, or with other materials, instruments and tools, they have priority over the coating film ( ⁇ ) and prevent the coating film ( ⁇ ) from sticking or melting. be able to.
- FIG. 7 is a schematic view showing a state where the particles (P) are exposed from the coating film ( ⁇ ).
- the relationship between the thickness (T) of the coated film after drying and the particle size (R) of the particles (P) is preferred so that the particles (P) come into contact with other materials more preferentially than the coated film ( ⁇ ).
- T / R 0.6-2.5
- R is the volume average particle diameter ( ⁇ m) of the particles P) It is preferable to satisfy.
- the T / R is less than 0.6, most of the individual particles of the particles (P) protrude from the coating film ( ⁇ ), so that the particles (P) easily fall off, and the particles (P) This is not preferable because the particles (P) that do not exhibit sufficient effects or fall off are likely to be mixed into the process and cause quality problems. Moreover, when it exceeds 2.5, since the exposure from the coating film ((alpha)) of particle
- the effect was remarkable when the diameter of the primary particles of the particles (P) was 1 to 10 ⁇ m and the exposure density was 100 to 2.0 ⁇ 10 6 particles / mm 2 .
- the exposure density is preferably 1.0 ⁇ 10 3 to 2.0 ⁇ 10 5 pieces / mm 2 , and the exposure density is 5.0 ⁇ 10 3 to 2.0 ⁇ 10 4 pieces / mm 2 . Further preferred.
- the diameter of the primary particles is less than 1 ⁇ m, since the particles (P) are buried in the coating film ( ⁇ ), it is difficult to exert an effect that the particles (P) come into contact with priority.
- the diameter of the primary particles is more than 10 ⁇ m, it is difficult for the particles (P) to be stably present in the coating material for forming the coating film ( ⁇ ), resulting in poor economics of coating storage and coating.
- the exposure density of the particles (P) is less than 100 particles / mm 2 , the density is too low, so that the effect that the particles (P) come into contact with priority is difficult to be exhibited.
- the exposure density exceeds 2.0 ⁇ 10 6 particles / mm 2 , the amount of particles (P) in the coating film ( ⁇ ) is too large, and the coating film is easily peeled off, which makes coating difficult. Problems arise.
- the manufacturing method of the coating composition ( ⁇ ) used for forming the coating film ( ⁇ ) of the present invention is not particularly limited.
- a method of adding each coating film ( ⁇ ) forming component in water or an organic solvent, stirring with a disperser such as a disper, and dissolving, dispersing or crushing and dispersing can be mentioned.
- a known hydrophilic solvent or the like may be added, if necessary, in order to improve the solubility or dispersibility of each coating film ( ⁇ ) forming component.
- the resin (A1), the conductive pigment (B), and the rust-preventing pigment (C) may be added to the particles (D) as necessary.
- Various water-soluble or water-dispersible additives may be added as long as the aqueous property and coating property are not impaired.
- various water-soluble or water-dispersible rust preventives that do not take the form of pigments, surfactants such as antifoaming agents, anti-settling agents, leveling agents, wetting and dispersing agents, thickeners, viscosity adjustments An agent or the like may be added.
- the coating film ( ⁇ ) of the present invention is formed from the aqueous coating composition ( ⁇ ), since it is aqueous, the surface tension is higher than that of the organic solvent coating composition, and the metal plate as the substrate (If there is a base treatment, the base treatment layer), conductive pigment (B), rust preventive pigment (C), inferior wettability to particles (D), etc., when applying a predetermined amount to the substrate, Uniform paintability and particle dispersibility may not be obtained. In such a case, it is preferable to add the above-mentioned wetting and dispersing agent or thickener.
- a surfactant that lowers the surface tension can be used, but it is better to use a polymer surfactant (polymer dispersant) having a molecular weight of 2000 or more.
- Low molecular surfactants can move relatively easily through moisture-containing resin coatings, so that water adsorbed on polar groups of surfactants and corrosive factors such as dissolved oxygen and dissolved salts can be removed via the water. It is easy to attract to the metal surface, and bleeds out on its own, so that it is easy to elute and often deteriorates the rust prevention property of the coating film.
- polymer surfactants can be adsorbed on the surface of metals, ceramic particles and pigments at multiple points, so that they are difficult to separate once adsorbed, and are effective in improving wettability even at low concentrations.
- the molecules are bulky, it is difficult to move through the resin coating film, and it is difficult to attract the corrosion factor to the metal surface.
- Part of the acrylic resin recommended to be added to the organic resin (A) in the section ⁇ Organic resin (A)> has the function of such a polymer surfactant, and is used for water-based coating.
- the conductive pigment (B), the rust preventive pigment (C), the particles (D) and the like are prevented from being settled and uniformly dispersed.
- Thickener is sufficient when wetting and dispersing agent alone does not provide sufficient surface coverage for the repellent area of the substrate surface, or the viscosity of the aqueous coating composition is too low to ensure the required coating thickness It can be added as a countermeasure when not. Many have a molecular weight of several thousand to several tens of thousands, adsorbed on the surface of pigments and the like, and the thickeners themselves associate with each other to form a weak network structure, thereby increasing the viscosity of the coating composition.
- the aqueous coating composition ( ⁇ ) contains conductive pigment (B), rust preventive pigment (C), and particles (D) with high specific gravity, if necessary, impart thixotropic properties (thixotropic properties) to the paint. It is better to add a viscosity modifier that can be used. As in the case of the thickener, the viscosity modifier is adsorbed on the surface of a pigment or the like in the aqueous coating composition to form a network structure. Since the molecular weight of such a viscosity modifier is very high at hundreds of thousands to millions, it forms a strong network structure with a large yield value in the aqueous coating composition ( ⁇ ), and thus the coating composition.
- an organic solvent-based coating composition ( ⁇ ) a coating composition in which a resin is dissolved in an organic solvent has a relatively high viscosity and is easy to adjust the viscosity. Therefore, the viscosity of the coating composition can be easily and stably maintained at 100 mPa ⁇ s or more, which is advantageous for suppressing pigment settling.
- non-oxide ceramics used as conductive materials are substances that also have hydrophobic sites on the surface, they are generally easy to disperse in organic solvent-based coating compositions ( ⁇ ), and coating Since the conductive pigment (B) in the coating composition ( ⁇ ) can sometimes be coated without settling, it is preferable.
- a coating composition having an organic solvent-based coating composition ( ⁇ ) forming a coating film having a viscosity of 100 to 2000 mPa ⁇ s is applied onto a metal plate with a roll coater or a curtain coater and then dried and baked
- the conductive pigment (B) is more preferable because it is difficult to settle.
- the viscosity of the coating composition ( ⁇ ) is less than 100 mPa ⁇ s, the conductive pigment (B) tends to settle, and when it exceeds 2000 mPa ⁇ s, the viscosity is too high and is generally referred to as living etc. May cause poor appearance. More preferably, it is 250 to 1000 mPa ⁇ s.
- the viscosity of the organic solvent-based coating composition ( ⁇ ) can be measured using a B-type viscometer at the same temperature as that of the coating composition when applied by a roll coater or a curtain coater.
- Viscosity can be adjusted by the type of organic solvent used and the amount of solvent.
- the organic solvent generally known solvents can be used, but organic solvents having a high boiling point are preferable. In the metal plate production line of the present invention, since the baking time is short, if a solvent having a low boiling point is used, there is a possibility that a coating defect generally called boiling will occur. It is preferable to use a solvent having a boiling point of 120 ° C. or higher.
- known solvents such as cyclohexane and aromatic hydrocarbon organic solvent Solvesso (product name of ExxonMobil Co., Ltd.) can be used.
- the coating film ( ⁇ ) of the present invention is a roll coat or groove roll when the coating composition ( ⁇ ) is an aqueous or organic solvent composition.
- a coating method such as coating, curtain flow coating, roller curtain coating, dipping (dip), air knife drawing, etc.
- the coating composition ( ⁇ ) is applied on the metal plate.
- a film forming method for drying the solvent is preferred.
- moisture or solvent is dried, and ultraviolet rays or electron beams are applied. It is preferable to polymerize by irradiation.
- the baking drying method in the case where the coating composition ( ⁇ ) is a water-based or organic solvent-based baking curable composition will be specifically described.
- the baking and drying method is not particularly limited, either by heating the metal plate in advance or heating the metal plate after application, Or you may dry these combining these.
- limiting in particular in a heating method A hot air, induction heating, near infrared rays, a direct fire, etc. can be used individually or in combination.
- the coating composition ( ⁇ ) is a water-based baking curable composition
- it is preferably 120 ° C. to 250 ° C. at the metal plate surface arrival temperature.
- the coating film is not sufficiently cured and the corrosion resistance may be lowered.
- the temperature exceeds 250 ° C. the bake hardening becomes excessive, and the corrosion resistance and the moldability may be lowered.
- the baking and drying time is preferably 1 to 60 seconds, and more preferably 3 to 20 seconds. If it is less than 1 second, the bake hardening is insufficient and the corrosion resistance may be lowered, and if it exceeds 60 seconds, the productivity may be lowered.
- the metal plate surface arrival temperature is preferably 180 ° C. to 260 ° C.
- the coating film is not sufficiently cured, and the corrosion resistance may be lowered.
- the temperature exceeds 260 ° C. the bake hardening becomes excessive, and the corrosion resistance and formability may be lowered.
- the baking and drying time is preferably 10 to 80 seconds, and more preferably 40 to 60 seconds. If it is less than 10 seconds, the bake hardening is insufficient and the corrosion resistance may be lowered, and if it exceeds 80 seconds, the productivity may be lowered.
- the coating composition ( ⁇ ) is a water-based or organic solvent-based ultraviolet curable composition or electron beam curable composition
- the moisture and solvent content of the wet coating film are dried, and then irradiated with ultraviolet rays or electron beams. Since the coating film is cured and formed mainly from radicals generated by irradiation with ultraviolet rays or electron beams, the drying temperature may be lower than that for the bake curable composition. In the drying process, it is preferable to irradiate with ultraviolet rays or electron beams after volatilizing most of moisture and solvent at a relatively low metal surface reaching temperature of about 80 to 120 ° C.
- the UV irradiation for radical polymerization of the UV curable resin in the coating film by UV irradiation and curing is usually performed in an air atmosphere, in an inert gas atmosphere, in a mixed atmosphere of air and an inert gas, or the like.
- the adhesion to the conductive pigment (B) and the metal plate surface is increased, and as a result, the corrosion resistance of the coating film is improved as compared with the case of ultraviolet curing in the air atmosphere.
- the inert gas used here include nitrogen gas, carbon dioxide gas, argon gas, and mixed gas thereof.
- the ultraviolet light source can be irradiated with ultraviolet rays by using, for example, a metal vapor discharge type high pressure mercury lamp, a metal halide lamp, a rare gas discharge type xenon lamp, an electrodeless lamp using microwaves, or the like.
- any lamp may be used as long as the ultraviolet curable coating film can be sufficiently cured and desired resistance weldability, corrosion resistance, and formability can be obtained.
- the peak illuminance and integrated light intensity of the ultraviolet rays received by the coating film influence the curability of the coating film, but the UV curing type coating film can be sufficiently cured, and the desired corrosion resistance and moldability can be obtained. If there is, ultraviolet irradiation conditions are not particularly limited.
- the coating composition ( ⁇ ) is an electron beam curable composition
- a normal electron beam irradiation apparatus used in the fields of printing, painting, film coating, packaging, sterilization, etc. is used for electron beam curing. be able to. These are accelerated by applying a high voltage to thermoelectrons generated from a hot filament in a high vacuum, and the resulting electron stream is taken out in an inert gas atmosphere and irradiated to a polymerizable substance.
- any apparatus may be used as long as the electron beam curable coating film can be sufficiently cured and desired resistance weldability, corrosion resistance, and formability can be obtained.
- the acceleration voltage of the electron beam absorbed by the coating film affects the depth at which the electron beam penetrates the coating film, and the absorbed dose affects the polymerization rate (curability of the coating film).
- the irradiation conditions of the electron beam are not particularly limited as long as the coating film of the mold can be sufficiently cured and desired corrosion resistance and moldability can be obtained.
- the inert gas used here include nitrogen gas, carbon dioxide gas, argon gas, and mixed gas thereof.
- Example I Hereinafter, the present invention will be specifically described by Example I using a water-based coating composition.
- Preparation of metal plate Prepare the following five types of galvanized steel sheets and immerse them in a 2.5% by weight, 40 ° C aqueous solution of an aqueous alkaline degreasing agent (FC-301 manufactured by Nihon Parkerizing Co., Ltd.) for 2 minutes. After degreasing, it was washed with water and dried to obtain a metal plate for painting.
- FC-301 aqueous alkaline degreasing agent manufactured by Nihon Parkerizing Co., Ltd.
- EG electrogalvanized steel sheet (plate thickness 0.8 mm, plating adhesion 30 g / m 2 )
- ZL Electric Zn-10% Ni alloy plated steel sheet (plate thickness 0.8 mm, plating adhesion 30 g / m 2 )
- GI Hot dip galvanized steel sheet (plate thickness 0.8 mm, plating adhesion 40 g / m 2 ) SD: Hot-dip Zn-11% Al-3% Mg-0.2% Si alloy-plated steel sheet (plate thickness 0.8 mm, plating deposit 40 g / m 2 )
- GA Alloyed hot-dip galvanized steel sheet (plate thickness 0.8 mm, 10% Fe, plating adhesion 45 g / m 2 )
- an aqueous coating composition comprising a polyester resin, silica fine particles, and a silane coupling agent was prepared.
- the above composition was bar-coated on the above-mentioned metal plate for coating so as to have a film thickness of 0.08 ⁇ m, dried in a hot air oven at a metal surface reaching temperature of 70 ° C., and air-dried.
- Resin (A1) Commercially available resins A1 to A8 shown in Table 1 were prepared as examples (invention examples) and comparative examples.
- Conductive pigment (B) Commercially available fine particles (reagents) shown in Table 2 were used (Examples). The volume average particle diameter was measured using Multisizer 3 (precision particle size distribution measuring apparatus based on the Coulter principle) manufactured by Beckman Coulter, Inc. The electrical resistivity is 80 mm long, 50 mm wide, and 2 to 4 mm thick sintered plate made from each fine particle. Resistivity meter Loresta EP (MCP-T360 type) manufactured by Mitsubishi Chemical Analytech Co., Ltd. and ESP The measurement was performed at 25 ° C. in accordance with JIS K7194 by a four-terminal four-probe method using a probe (diameter 2 mm of the flat head of the terminal) and a constant current application method.
- Multisizer 3 precision particle size distribution measuring apparatus based on the Coulter principle
- the electrical resistivity is 80 mm long, 50 mm wide, and 2 to 4 mm thick sintered plate made from each fine particle.
- Resistivity meter Loresta EP M
- TiB TiB 2 fine particles (TII11PB manufactured by Purifying Research Institute Co., Ltd., volume average diameter 2.9 ⁇ m, electrical resistivity 30 ⁇ 10 ⁇ 6 ⁇ cm)
- ZrB ZrB 2 fine particles (manufactured by Wako Pure Chemical Industries, Ltd., volume average diameter 2.2 ⁇ m, electrical resistivity 70 ⁇ 10 ⁇ 6 ⁇ cm)
- MoB Mo 2 B fine particles (manufactured by Mitsuwa Chemical Co., Ltd., dimolybdenum boride, volume average diameter 5.2 ⁇ m, electrical resistivity 30 ⁇ 10 ⁇ 6 ⁇ cm)
- LaB LaB 6 fine particles (Zeon Boron, lanthanum hexaboride, volume average diameter 2.8 ⁇ m, electrical resistivity 20 ⁇ 10 ⁇ 6 ⁇ cm)
- VC VC fine particles (manufactured by Wako Pure Chemical Industries, Ltd., volume average diameter 2.3 ⁇ m, electrical resistivity 140 ⁇ 10
- SUS SUS304 particles (volume average diameter 3.3 ⁇ m, electrical resistivity 70 ⁇ 10 ⁇ 6 ⁇ cm)
- ZrB + VC mixture of ZrB and VC (volume ratio 1: 1)
- ZrB + TiC mixture of ZrB and TiC (volume ratio 1: 1)
- VC + TiN mixture of VC and TiN (volume ratio 1: 1)
- Rust prevention pigment Commercially available reagents shown in Table 3 and Table 4, industrial products, or blends thereof were used (Examples).
- aqueous coating compositions were prepared at various blending ratios using the resin (A), conductive pigment (B), rust preventive pigment (C), particles (D) and distilled water.
- the concentration of the non-volatile content of the water-based coating composition was appropriately adjusted by changing the amount of water added in order to obtain the target coating amount and good coating properties.
- the “nonvolatile content” means a component remaining after volatilizing water and organic solvents mixed as a solvent in the paint or composition.
- Table 6 shows the component composition and the content (volume fraction%) in the coating film of the coating film ( ⁇ ) prepared using the coating film constituent components.
- each component is uniformly dispersed, it is applied to the metal plate for coating or a metal plate provided with a base treatment film using a roll coater, and this is applied to the metal surface in a hot air oven. It was dried at an ultimate temperature of 200 ° C., water-cooled and air-dried.
- Table 7 shows the coating thickness ( ⁇ m unit) after film formation. The coating thickness was calculated by dividing the mass difference before and after peeling of the coating after coating by the specific gravity of the coating. The specific gravity of the coating film was calculated from the blending amount of the coating film components and the known specific gravity of each component.
- Table 6 shows the HM distribution at ⁇ 20 ° C. and the HM distribution at 40 ° C. on the surface of the coating film ( ⁇ ) on the surface of the coated metal plate.
- Each distribution state is shown as follows.
- the measurement site is 60 points or more.
- (2) HM distribution at 40 ° C. 1 The measurement site where the micro Martens hardness HM at 40 ° C. is 200 to 200,000 mg / mm 2 is 0 points out of 100 random measurement points.
- Up to 4 point state 2 Measurement site with HM of 200 to 200000 mg / mm 2 5 to 9 point State 3: Measurement site with HM of 200 to 200000 mg / mm 2 10 to 19 points
- State 4 20 or more measurement sites with HM of 200 to 200,000 mg / mm 2
- Number of hit points is 1000 points or more 3: 200 points or more, less than 1000 points 2: less than 200 points 1: Nugget is not generated and one point cannot be welded
- test pieces cut to 50 mm x 50 mm are stacked so that the front and back surfaces are in surface contact with each other, and subjected to hot pressing at 40 ° C for 100 kg / cm 2 ⁇ 24 hours. Thereafter, the degree of stacking (sticking) of the coating film was evaluated according to the following criteria.
- Table 7 (Tables 7-1 and 7-2) shows the evaluation results.
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Abstract
Description
[1]
金属板、および前記金属板の少なくとも一方の表面上にある塗膜(α)を含む自動車用塗装金属板であって、
前記塗膜(α)が、有機樹脂(A)と、導電性顔料(B)と、防錆顔料(C)とを含み、
塗膜(α)表面の-20℃における微小マルテンス硬度が、100点測定した際に20点以上がHM10~200(mg/mm2)であり、塗膜(α)表面の40℃における微小マルテンス硬度が、100点測定した際に5点以上がHM200~200000(mg/mm2)である、自動車用塗装金属板。
[2]
前記有機樹脂(A)のガラス転移温度Tgが、-80℃~-20℃である、[1]に記載の自動車用塗装金属板。
[3]
前記有機樹脂(A)が、ポリエステル樹脂、ポリウレタン樹脂、アクリル樹脂、またはそれらの変性体から成る群より選ばれる、[1]に記載の自動車用塗装金属板。
[4]
前記導電性顔料(B)が、硼化物、炭化物、窒化物、珪化物の少なくとも1種から選ばれる、25℃の電気抵抗率が0.1×10-6~185×10-6Ωcmの非酸化物セラミックス粒子である、[1]に記載の自動車用塗装金属板。
[5]
前記塗膜(α)が、0.5vol%~65vol%の量の導電性顔料(B)を含有する、[1]に記載の自動車用塗装金属板。
[6]
前記防錆顔料(C)が、珪酸イオン、燐酸イオン、バナジン酸イオン、タングステン酸イオン、又はモリブデン酸イオンを放出できる化合物、およびまたはSi、Ti、Al、およびZrからなる群より選ばれる金属元素を含む粒子から選ばれる1種または2種以上を含む、[1]に記載の自動車用塗装金属板。
[7]
前記塗膜(α)が、1vol%~40vol%の量の防錆顔料(C)を含有する、[1]に記載の自動車用塗装金属板。
[8]
40℃でのマルテンス硬度が200mg/mm2~200000mg/mm2の粒状の粒子(D)を塗膜中に含む、[1]に記載の自動車用塗装金属板。
[9]
[1]に記載の自動車用塗装金属板を加工、成形して形成された自動車部品。
[10]
[9]に記載の自動車部品に、さらに電着塗膜層、中塗り塗膜層、上塗り塗膜層のうちいずれか一層以上を塗布して形成された自動車部品。
本発明の自動車用塗装金属板は、特定の導電性塗膜で表面の少なくとも一部が被覆された、例えばめっき皮膜つき金属板である。当該金属板は、用途に応じ、金属板の両面が導電性塗膜で被覆されていても、片面のみが被覆されていてもよく、また、表面の一部が被覆されていても、全面が被覆されていてもよい。金属板の導電性塗膜で被覆された部位は抵抗溶接性、耐食性が優れるものである。
本発明の金属板を被覆する塗膜(α)は、有機樹脂(A)と、導電性顔料(B)と、防錆顔料(C)とを含み、塗膜(α)表面の-20℃における微小マルテンス硬度が、100点測定した際に20点以上がHM10~200(mg/mm2)であり、塗膜(α)表面の40℃における微小マルテンス硬度が、100点測定した際に5点以上がHM200~200000(mg/mm2)である。
本発明の有機樹脂(A)は、塗膜(α)のバインダー成分であり、これを適宜選択することにより、本発明の自動車用塗装金属板の塗膜に必要な-20℃での微小マルテンス硬度HM及びTgを得ることができる。有機樹脂(A)は、水系、有機溶剤系樹脂のいずれでもよく、特に、後述する樹脂(A1)である。有機樹脂(A)は、更に追加して樹脂(A1)の反応誘導体(A2)を含むことができる。
前記有機樹脂(A)のガラス転移温度Tgは-80℃~-20℃であることが好ましい。ガラス転移温度Tgは、塗膜を形成する有機樹脂を、到達温度200℃で加熱硬化することで膜厚15μmのフィルムを形成し、示差走査熱量計(DSC)のピーク温度又は動的粘弾性測定機装置での転移温度として測定することができる。Tgは-80℃以上-20℃以下であることが好ましい。-20℃よりもTgの高い樹脂は、柔軟性が低いため石跳ねの衝突による塗膜の傷付きに伴い解放される塗膜の収縮応力がめっき層に伝わることを緩和する能力が小さい。Tgの下限は特に定めるところではないが、-80℃を超えて低いTgを有する有機樹脂は、工業的に安価に入手しにくい。さらに、Tgは-60℃以上-30℃以下であることが好ましい。
導電性顔料(B)としては、金属、合金、導電性炭素、燐化鉄、炭化物、半導体酸化物の中から選ばれる1種以上を用いることが好ましい。例えば、亜鉛、ニッケル、鉄、アルミニウム、コバルト、マンガン、銅、錫、クロムなどの金属またはそれらの合金粉末、導電性カーボン、黒鉛粉末などの導電性炭素粉末、燐化鉄粉末、炭化チタン、炭化珪素などの炭化物粉末、導電性半導体粉末、セラミクス粒子等を挙げることができる。これらの中でも、本発明の塗装金属板においては、非酸化物セラミクス粒子が、特に好ましい。
本発明に用いる防錆顔料(C)の種類としては特に限定されないが、珪酸塩化合物、燐酸塩化合物、バナジン酸塩化合物、および金属酸化物微粒子から選ばれる1種または2種以上を含むのが好ましい。
上記導電性顔料(B)、防錆顔料(C)に加え、本発明の塗膜中の粒子として、40℃でのマルテンス硬度が200mg/mm2~200000mg/mm2の粒状の、ワックスや樹脂ビーズ等の粒子(D)を含んでいてもよい。40℃でのマルテンス硬度が200mg/mm2~200000mg/mm2の粒状のワックスや樹脂ビーズは、塗料への添加の容易性などを考慮して任意に選択できる。例えば、ポリオレフィンワックス、ポリエチレンワックス、ポリプロピレンワックス、ポリブチレンワックス、変性ポリオレフィンワックス、アクリル樹脂粒子、シリコーン樹脂粒子、弗素樹脂粒子、ポリアクリロニトリル樹脂等を用いることができる。
T/R=0.6~2.5
(式中、Rは前記粒子Pの体積平均粒径(μm)である)
を満たすことが好ましい。T/Rが、0.6未満であると、粒子(P)の個々の粒子の大部分が塗膜(α)から突出しているために粒子(P)が脱落しやすく、粒子(P)が十分に効果を発揮しない、あるいは脱落した粒子(P)が工程に混入して品質上の問題を生じやすくなるため好ましくない。また、2.5を超えると、粒子(P)の塗膜(α)からの露出が不十分で、粘着あるいは溶融することを防止する効果が低いため好ましくない。
本発明の塗膜(α)を形成するのに用いる塗装用組成物(β)の製造方法は特に限定されない。例えば、水中または有機溶剤中に各々の塗膜(α)形成成分を添加し、ディスパー等の分散機で攪拌し、溶解、分散もしくは破砕分散する方法が挙げられる。水系塗装用組成物の場合、各々の塗膜(α)形成成分の溶解性、もしくは分散性を向上させるために、必要に応じて、公知の親水性溶剤等を添加してもよい。
本発明の前記塗膜(α)は、<塗膜(α)>の項で述べたように、塗装用組成物(β)が水系や有機溶剤系組成物の場合は、ロールコート、グルーブロールコート、カーテンフローコート、ローラーカーテンコート、浸漬(ディップ)、エアナイフ絞り等の公知の塗装方法を用いて、金属板上に塗装用組成物(β)を塗布し、その後、ウェット塗膜の水分や溶剤分を乾燥する製膜方法が好ましい。これらのうち、水系や有機溶剤系の紫外線硬化型組成物や電子線硬化型組成物の場合は、前記の塗布方法で金属板に塗布後、水分または溶剤分を乾燥し、紫外線や電子線を照射して重合させるのが好ましい。
以下、水系塗装用組成物を用いた実施例Iにより本発明を具体的に説明する。
以下の5種の亜鉛系めっき鋼板を準備し、水系アルカリ脱脂剤(日本パーカライジング(株)製FC-301)の2.5質量%、40℃水溶液に2分間浸漬して表面を脱脂した後、水洗、乾燥して塗装用の金属板とした。
ZL:電気Zn-10%Ni合金めっき鋼板(板厚0.8mm、めっき付着量30g/m2)
GI:溶融亜鉛めっき鋼板(板厚0.8mm、めっき付着量40g/m2)
SD:溶融Zn-11%Al-3%Mg-0.2%Si合金めっき鋼板(板厚0.8mm、めっき付着量40g/m2)
GA:合金化溶融亜鉛めっき鋼板(板厚0.8mm、10%Fe、めっき付着量45g/m2)
<塗膜(α)>の項で述べたように、本発明においては、塗膜(α)と金属板表面の間に必ずしも下地処理皮膜を設ける必要はないが、塗膜(α)の金属板への密着性や耐食性等を更に改善するために用いることがある。ここでは、一部の塗装用金属板に下地処理皮膜を設けて評価した。
水系塗装用組成物の調製のため、まず、樹脂(A)、導電性顔料(B)、防錆顔料(C)を準備した。
表1に示す樹脂A1~A8の市販の樹脂を、実施例用(発明例)、比較例用樹脂として準備した。
表2に示す市販の微粒子(試薬)を用いた(実施例)。体積平均粒径は、ベックマン・コールター(株)製Multisizer3(コールター原理による精密粒度分布測定装置)を用いて測定した。電気抵抗率は、各微粒子から長さ80mm、幅50mm、厚さ2~4mmの焼結板を作成し、(株)三菱化学アナリテック製の抵抗率計ロレスタEP(MCP-T360型)とESPプローブ(端子の平頭部の直径2mm)を用いた4端子4探針法、定電流印加方式で、JIS K7194に準拠して25℃で測定した。
ZrB:ZrB2微粒子(和光純薬工業(株)製、体積平均径2.2μm、電気抵抗率70×10-6Ωcm)
MoB:Mo2B微粒子(三津和化学薬品(株)製ほう化二モリブデン、体積平均径5.2μm、電気抵抗率30×10-6Ωcm)
LaB:LaB6微粒子(添川理化学(株)製六硼化ランタン、体積平均径2.8μm、電気抵抗率20×10-6Ωcm)
VC:VC微粒子(和光純薬工業(株)製、体積平均径2.3μm、電気抵抗率140×10-6Ωcm)
TiC:TiC微粒子(和光純薬工業(株)製、体積平均径3.2μm、電気抵抗率180×10-6Ωcm)
TiN:TiN微粒子(和光純薬工業(株)製、体積平均径1.6μm、電気抵抗率20×10-6Ωcm)
NiSi:Ni2Si微粒子((株)高純度化学研究所製NII11PBを水に添加し攪拌、懸濁させ、5分経過後になお浮遊する微小粒子を濾別して使用。体積平均径4.8μm、電気抵抗率40×10-6Ωcm)
SUS:SUS304粒子(体積平均径3.3μm、電気抵抗率70×10-6Ωcm)
ZrB+VC:前記ZrBと前記VCの混合物(体積比1:1)
ZrB+TiC:前記ZrBと前記TiCの混合物(体積比1:1)
VC+TiN:前記VCと前記TiNの混合物(体積比1:1)
表3、表4に示す市販の試薬、工業製品、またはこれらをブレンドして用いた(実施例)。
表5に示す市販の工業製品を用いた(実施例)。
(1)-20℃でのHM分布
状態1:-20℃における微小マルテンス硬度HMが10~200mg/mm2である測定部位が、無作為な測定点数100点のうち0~19点
状態2:HMが10~200mg/mm2である測定部位が、20点~39点
状態3:HMが10~200mg/mm2である測定部位が、40点~59点
状態4:HMが10~200mg/mm2である測定部位が、60点以上
(2)40℃でのHM分布
状態1:40℃における微小マルテンス硬度HMが200~200000mg/mm2である測定部位が、無作為な測定点数100点のうち0点~4点
状態2:HMが200~200000mg/mm2である測定部位が、5点~9点
状態3:HMが200~200000mg/mm2である測定部位が、10点~19点
状態4:HMが200~200000mg/mm2である測定部位が、20点以上
前記3.の方法で作成した塗装金属板を用い、溶接性、耐食性、耐チッピング性、チッピング後耐食性及び耐スタック性について評価を行った。以下に、各試験と評価の方法を示す。
先端径5mm、R40のCF型Cr-Cu電極を用い、加圧力1.96kN、溶接電流8kA、通電時間12サイクル/50Hzにてスポット溶接の連続打点性試験を行い、ナゲット径が3√t(tは板厚)を切る直前の打点数を求めた。以下の評価点を用いてスポット溶接性の優劣を評価した。
3:200点以上、1000点未満
2:200点未満
1:ナゲットが生成せず1点も溶接できない
前記3.の方法で作成した塗装金属板から150×70mmサイズの長方形の試験片を切り出し、端部を樹脂シールして平面部耐食性の試験片とした。
3:300サイクルで赤錆発生なし
2:150サイクルで赤錆発生なし
1:150サイクルで赤錆発生あり
前記3.の方法で作成した塗装金属板から150×70mmサイズの長方形の試験片を切り出し、耐チッピング性の試験片とした。試験片は電着塗装(膜厚15μm)、中塗塗装(膜厚30μm)・上塗塗装(膜厚30μm)を施した。上記塗済の鋼板に気温-15℃の室内で空気圧にて時速30~60km/hの速度に加速した砕石(玄武岩、粒径5~7.5mm)を100個射出し試験板の平面を、砕石の飛来方向に対して15度傾けて衝突させた。砕石の衝突の中心部20×20mmの範囲を観察し、以下の評価点を用いて加工部耐食性の優劣を評価した。
3:めっき鋼板の地鉄が長径と短径の平均で100μm以上のサイズで1箇所露出
2:めっき鋼板の地鉄が長径と短径の平均で100μm以上のサイズで2~4箇所露出
1:めっき鋼板の地鉄が長径と短径の平均で100μm以上のサイズで5箇所以上露出
前記(4)の方法で傷つけた塗装金属板を、チッピング後耐食性の試験片とした。
3:30~59サイクルで錆汁が目視でわかる赤錆発生あり
2:13~29サイクルで錆汁が目視でわかる赤錆発生あり
1:12サイクルで錆汁が目視でわかる赤錆発生あり
作製した塗装金属板のおもて面とその反対面であるうら面を加圧下に面接触させて、耐スタック性を評価した。
2:塗膜同士がややスタックしているが、簡単に手でかるくはがせる程度、
1:塗膜同士がスタックしており、手で容易にはがせない程度。
Claims (10)
- 金属板、および前記金属板の少なくとも一方の表面上にある塗膜(α)を含む自動車用塗装金属板であって、
前記塗膜(α)が、有機樹脂(A)と、導電性顔料(B)と、防錆顔料(C)とを含み、
塗膜(α)表面の-20℃における微小マルテンス硬度が、100点測定した際に20点以上がHM10~200(mg/mm2)であり、塗膜(α)表面の40℃における微小マルテンス硬度が、100点測定した際に5点以上がHM200~200000(mg/mm2)である、自動車用塗装金属板。 - 前記有機樹脂(A)のガラス転移温度Tgが、-80℃~-20℃である、請求項1に記載の自動車用塗装金属板。
- 前記有機樹脂(A)が、ポリエステル樹脂、ポリウレタン樹脂、アクリル樹脂、またはそれらの変性体から成る群より選ばれる、請求項1に記載の自動車用塗装金属板。
- 前記導電性顔料(B)が、硼化物、炭化物、窒化物、珪化物の少なくとも1種から選ばれる、25℃の電気抵抗率が0.1×10-6~185×10-6Ωcmの非酸化物セラミックス粒子である、請求項1に記載の自動車用塗装金属板。
- 前記塗膜(α)が、0.5vol%~65vol%の量の導電性顔料(B)を含有する、請求項1に記載の自動車用塗装金属板。
- 前記防錆顔料(C)が、珪酸イオン、燐酸イオン、バナジン酸イオン、タングステン酸イオン、又はモリブデン酸イオンを放出できる化合物、およびまたはSi、Ti、Al、およびZrからなる群より選ばれる金属元素を含む粒子から選ばれる1種または2種以上を含む、請求項1に記載の自動車用塗装金属板。
- 前記塗膜(α)が、1vol%~40vol%の量の防錆顔料(C)を含有する、請求項1に記載の自動車用塗装金属板。
- 40℃でのマルテンス硬度が200mg/mm2~200000mg/mm2の粒状の粒子(D)を塗膜中に含む、請求項1に記載の自動車用塗装金属板。
- 請求項1に記載の自動車用塗装金属板を加工、成形して形成された自動車部品。
- 請求項9に記載の自動車部品に、さらに電着塗膜層、中塗り塗膜層、上塗り塗膜層のうちいずれか一層以上を塗布して形成された自動車部品。
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Also Published As
Publication number | Publication date |
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PL3202569T3 (pl) | 2020-06-15 |
CA2962729C (en) | 2019-08-06 |
CN107000379A (zh) | 2017-08-01 |
CN107000379B (zh) | 2019-10-25 |
ES2757305T3 (es) | 2020-04-28 |
KR20170060088A (ko) | 2017-05-31 |
EP3202569A1 (en) | 2017-08-09 |
JPWO2016052661A1 (ja) | 2017-07-20 |
EP3202569B1 (en) | 2019-09-11 |
JP6466954B2 (ja) | 2019-02-06 |
KR101979520B1 (ko) | 2019-05-17 |
CA2962729A1 (en) | 2016-04-07 |
US10913860B2 (en) | 2021-02-09 |
RU2656031C1 (ru) | 2018-05-30 |
US20170298231A1 (en) | 2017-10-19 |
EP3202569A4 (en) | 2018-04-04 |
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