Classifications

• • 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
  • B05D1/00—Processes for applying liquids or other fluent materials
  • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
• • 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
  • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
  • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
• • 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
  • B05D7/24—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 for applying particular liquids or other fluent materials
• • 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
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
  • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D201/00—Coating compositions based on unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives

Definitions

• the present invention relates to a metallic paint composition.
• Metallic paints containing glitter pigments are known as means for imparting a glittering metallic design to a substrate.
• a metallic paint containing a scaly aluminum pigment (brightness pigment) produced by a vapor deposition method and a nitrocellulose-based resin in a solvent is used for an aluminum wheel (base material).
• This metallic paint uses scaly aluminum pigments as a glittering pigment, so it is possible to give a metallic design with a high glittering feeling with a fine finish that does not give the feeling of aluminum particles to the substrate. It is.
• This metallic paint is applied with a thin coating film thickness (for example, 2 to 3 ⁇ m) in order to improve the orientation of the scaly aluminum pigment in the coating film and obtain a glittering feeling.
• Patent Document 1 describes a primerless paint containing a luster pigment, a solvent, and a coating film forming element (a pigment-supporting polymer containing nitrocellulose or acetylbutylcellulose and an acrylic urethane resin).
• the covering power of the coating film is low and the color of the base is easy to see through.
• the present inventor has found that it is necessary to apply a base coat (base black) in advance.
• a colored pigment may be mix
• a paint containing a colored pigment having a large particle size for example, 5 ⁇ m
• a thin coating film thickness for example, 2 to 3 ⁇ m
• the smoothness of the coating film is caused by the presence of the colored pigment larger than the coating film thickness.
• the present inventor has found that color blur (cannot be stably colored) and irregular reflection occur, resulting in a loss of glitter (metal feeling). Furthermore, (1) The nitrocellulose resin contained in this metallic paint has a narrow range of choices of usable solvents, and the usable solvent (for example, butyl acetate) has low solubility and the light resistance of the coating film. (2) The yellowing of the coating film is caused by a decrease in color difference (yellowing) and a decrease in gloss retention, and a problem of causing a decrease in the appearance of the coating film due to a decrease in weather resistance. The present inventor has found that this occurs when the nitrocellulose-based resin turns yellow when the coating film is dried (for example, baking coating at 150 ° C.).
• the aforementioned primerless metallic paint contains a cellulosic resin.
• this cellulosic resin has a problem that the compatibility with the clear paint, which occurs when the coating film is thinned, and the light resistance of the coating film are lowered. The inventor found that there is.
• a metallic paint comprising a combination of a scaly glittering pigment, a resin having a predetermined weight average molecular weight and a glass transition point (Tg), and a solvent is described below.
• Tg glass transition point
• the clear paint can be applied on the metallic paint without heating and drying (B) (wet-on-wet paint).
• B heating and drying
• the coating film of the above (1) can be obtained even when coated with a thick coating film thickness, even if a colored pigment having a large particle diameter is further blended, the smoothness of the coating film is not impaired, and color blurring and irregular reflection are caused. It is hard to happen.
• the thickness of the aluminum flake pigment is 0.01 to 0.5 ⁇ m, [1] to [2], wherein the particle diameter (D50) of the aluminum flake pigment is 5 to 20 ⁇ m, and the difference between the particle diameter (D90) and the particle diameter (D10) of the aluminum flake pigment is 50 ⁇ m or less.
• a method for coating a base material using the metallic paint composition according to any one of [1] to [8] above comprising the following steps: (1) a step of applying a metallic coating composition on a substrate coated with a powder primer, and (2) The said coating method including the process of apply
• a coated body comprising a substrate having a coating film of the metallic paint composition according to any one of [1] to [8], Having a powder primer coating on the substrate, Having a coating film of the metallic coating composition on the coating film of the powder primer,
• the coated body comprising a coating film of a clear coating as an outermost layer on a coating film of the metallic coating composition.
• the metallic paint composition of the present invention can exhibit the following effects.
• (1) A metallic coating film having no unevenness on the surface of the coating film and having an improved surface concealing property can be obtained while maintaining the same brightness as that of the metallic coating film obtained by the conventional 3C3B coating method.
• the metallic paint composition of the present invention is Scaly glitter pigment; A resin having a weight average molecular weight of 40,000 to 60,000 and a glass transition point (Tg) of ⁇ 25 to 40 ° C .; Solvent.
• the scale-like glitter pigment means a pigment capable of giving off a metallic luster, and specific examples thereof include metal pigments (for example, aluminum pigments) and pigments obtained from natural mica (for example, pearls). Pigments) and glass flake pigments, preferably aluminum pigments and pearl pigments, more preferably aluminum pigments.
• Scale-like means a thin plate-like shape like a scale.
• the planar shape is not particularly limited, and may be a circle, an ellipse, a square, an indeterminate form, or the like. A circular shape is preferred in that it can be easily oriented in a parallel layer in the coating film.
• the scaly glittering pigment those used in the field of paints and inks can be used without particular limitation.
• the scale-like aluminum pigment an aluminum flake pigment produced by a pulverization method or a vapor deposition method can be suitably used.
• Aluminum flake pigments produced by a grinding method are preferred.
• the thickness of the aluminum flake pigment is preferably 0.01 to 0.5 ⁇ m, more preferably 0.01 to 0.3 ⁇ m, and the particle diameter (D50) of the pigment is preferably 5 to It is 20 ⁇ m, more preferably 7 to 18 ⁇ m.
• the aspect ratio (D50 / thickness) between the particle diameter (D50) and the thickness is preferably 10 to 2000, and more preferably 24 to 1800.
• the particle size distribution of the aluminum flake pigment is preferably such that the difference between the particle size (D90) and the particle size (D10) is smaller, and the difference in particle size between D90 and D10 is 50 ⁇ m or less, preferably 45 ⁇ m or less. preferable.
• the particle diameter is a value measured by laser diffraction or dynamic light scattering.
• the scaly glittering pigment is easily available in the market, but can also be prepared by a known method.
• Product name: Z485 manufactured by Toyo Aluminum Co., Ltd.
• Product name: 5680 NS manufactured by Toyo Aluminum Co., Ltd. Aluminum flake pigment paste produced by a pulverization method.
• Thickness 0.2 ⁇ m, particle diameter (D10): 5 ⁇ m, particle diameter (D50): 14.2 ⁇ m, particle diameter ( D90): 45.7 ⁇ m, aspect ratio (D50 / thickness): 71, difference between D90 and D10: 40.7 ⁇ m),
• Thickness 0.05 ⁇ m, particle diameter (D10): 5.7 ⁇ m, particle diameter (D50): 12.7 ⁇ m
• the scaly glittering pigment one kind may be used alone, or two or more kinds may be used in combination.
• the content of the scaly glittering pigment in the metallic coating composition is not particularly limited, but is preferably 1 to 4% by mass, more preferably 2 to 3% by mass, and particularly preferably based on the total mass of the metallic coating composition. 2.5 to 3% by mass. When the content is 1 to 4% by mass, the underlying color can be concealed higher.
• the resin used in the metallic coating composition of the present invention has a weight average molecular weight of 40,000 to 60,000, preferably 43,000 to 57,000, more preferably 45,000 to 55,000.
• weight average molecular weight is 40,000 or more
• the solvent evaporates from the paint the coating film becomes highly viscous and the fluidity is lowered, so that the scaly glittering pigment is easily oriented in the coating film, and the glittering feeling is improved.
• a high metallic design can be imparted to the substrate.
• the weight average molecular weight is 60000 or less, the viscosity of the metallic coating composition can be suppressed from excessively rising, and the coating workability can be kept good. Increasing the dilution rate may make it difficult to control the coating thickness).
• the weight average molecular weight is a value determined by a method of using polystyrene as a standard substance in gel permeation chromatography (GPC) and determining the molecular weight of the sample by relative comparison between the polystyrene and the sample.
• the measurement of the weight average molecular weight by GPC can be performed by the following method, for example. Using a TSKgel column (manufactured by Tosoh Corp.), it is determined by GPC equipped with RI (manufactured by Tosoh Corp .; HLC-8220 GPC).
• tetrahydrofuran is used as a developing solvent, and measurement is performed at a flow rate of 0.35 ml / min and a temperature of 40 ° C.
• TSK standard polystyrene manufactured by Tosoh Corporation is used as a standard substance.
• the resin used in the metallic coating composition of the present invention has a glass transition point (Tg) of ⁇ 25 to 40 ° C., preferably ⁇ 10 to 20 ° C., more preferably ⁇ 5 to 15 ° C.
• Tg glass transition point
• the glass transition point is ⁇ 25 ° C. or more
• the erosion is unlikely to occur (in other words, it has a high separation property with respect to the clear paint), so that the smoothness of the metallic layer can be maintained and the glittering feeling can be maintained.
• the clear paint can be applied without wet drying the metallic paint composition (wet-on-wet paint) by utilizing the high separation property with respect to the clear paint.
• the glass transition point is 40 ° C. or less, the impact resistance of the coating film formed from the metallic coating composition can be kept good.
• the glass transition point is a value measured by the plastic transition temperature measuring method in JISK7121.
• resins used in the field of paints and inks can be used without particular limitation.
• the nitrocellulose resin contained in the metallic paint of the prior art has a weight average molecular weight of about 300,000 and a glass transition point (Tg) of about 190 ° C., and thus does not correspond to the resin used in the present invention.
• the resin used in the present invention can be easily obtained on the market, but can also be prepared by a known method.
• the type of resin can be selected in consideration of the balance of drying properties, solvent selectivity and coating film performance, but it is easy to adjust the drying speed, the solvent selectivity is high (dissolvable in various solvents), and Polyurethane resin is preferable from the viewpoint that the coating film is hardly yellowed in the light resistance test.
• the polyurethane resin is preferably a lacquer type polyurethane resin that does not change the molecular weight in the steps of coating to heat drying and forms a coating film only by evaporation of the solvent.
• Examples of the lacquer type urethane resin include trade name: Bernock 16-416 (manufactured by DIC, weight average molecular weight: 50677, glass transition point (Tg): 0 ° C.).
• Bernock 16-416 becomes so viscous that stringing occurs when the concentration with respect to the total mass of the metallic coating composition exceeds 8% by mass, and the scaly glittering pigment is more easily oriented in the coating film.
• the resin satisfying the above-mentioned conditions of weight average molecular weight and glass transition point may be used alone or in combination of two or more.
• the content of the resin in the metallic coating composition is not particularly limited, but is preferably 1 to 30% by mass, more preferably 2 to 25% by mass, and particularly preferably 3 to 20% by mass with respect to the total mass of the metallic coating composition. It is. When the content is 1 to 30% by mass, the color of the base can be further concealed.
• solvent used in the metallic coating composition of the present invention functions as a solvent for the aforementioned “resin having a weight average molecular weight of 40,000 to 60,000 and a glass transition point (Tg) of ⁇ 25 to 40 ° C.”
• solvent can be used without particular limitation. Specific examples include acetate solvents, alcohol solvents, ether solvents, ester solvents, glycol ether solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, and the like.
• the solvent can be appropriately selected in consideration of drying properties, resin solubility, and the like. For example, methyl ethyl ketone, isopropyl alcohol, butyl acetate, or the like can be preferably used for the lacquer type urethane resin described above.
• Solvents may be used alone or in combination of two or more.
• Solvents are easily available on the market, but can also be prepared by known methods.
• the content of the solvent in the metallic coating composition is not particularly limited, but is preferably 65 to 90% by mass, more preferably 70 to 90% by mass, and particularly preferably 75 to 90% by mass with respect to the total mass of the metallic coating composition. It is. If it is 65 to 90% by mass, the color of the substrate can be concealed.
• a colored pigment may be blended in order to obtain a colored (colored) metallic coating film layer.
• the colored pigment those used in the field of paints and inks (for example, organic pigments and inorganic pigments) can be used without particular limitation.
• a colored pigment having a large particle diameter for example, 5 to 10 ⁇ m
• Colored pigments may be used alone or in combination of two or more.
• Colored pigments are easily available on the market, but can also be prepared by known methods.
• the content of the colored pigment in the metallic coating composition is not particularly limited as long as the blending purpose can be achieved, but it is preferably 1 to 4% by mass, more preferably 2 to 3% by mass, particularly with respect to the total mass of the metallic coating composition.
• the amount is preferably 2.5 to 3% by mass.
• a dispersant also referred to as an anti-settling agent
• an anti-settling agent can be added to the metallic paint composition of the present invention in order to improve the dispersibility of the scaly glittering pigment or the colored pigment.
• the dispersant those used in the field of paints and inks can be used without particular limitation.
• the content of the dispersant in the metallic coating composition is not particularly limited as long as the purpose of blending can be achieved, but it is preferably 1 to 4% by mass, more preferably 2 to 3% by mass, particularly with respect to the total mass of the metallic coating composition.
• the amount is preferably 2.5 to 3% by mass.
• the metallic coating composition of the present invention includes various additives generally used in metallic coating compositions (for example, anti-settling agents, sagging inhibitors, viscosity modifiers (thickeners)).
• a dehydrating agent, an antifoaming agent, an ultraviolet absorber, a light stabilizer, a surface conditioner, a low-contaminating agent, a catalyst, etc. can be appropriately blended.
• the method for producing the metallic coating composition of the present invention is not particularly limited. It can be produced by a known production method of a metallic coating composition, for example, by mixing each component with a disper.
• the metallic paint composition of the present invention can be used as a paint for imparting a metallic design having a glittering feeling to a substrate. Since the coating film formed from the metallic coating composition of the present invention has improved concealment of the base, the base coating (base black) applied by the conventional metallic coating method (3C3B method) is applied (C ) And drying by heating (B) can be omitted. Furthermore, since the metallic paint composition of the present invention has a good separation property with respect to the clear paint, the clear paint can be applied on the metallic paint without heating and drying (B).
• the coating method using the metallic paint composition of the present invention includes the following steps: (1) A step of coating (C) a metallic coating composition on a substrate coated with a powder primer, and (2) A two-coat one-bake (2C1B) method including a step of applying a clear paint (C) on a coating film of the metallic paint composition obtained in the step (1) and drying by heating (B). is there.
• the kind of the substrate to which the coating method of the present invention can be applied is not particularly limited as long as it is not affected by the solvent contained in the metallic paint composition.
• Specific examples of the substrate include metals (for example, iron and aluminum).
• metals for example, iron and aluminum.
• goods comprised from a base material, A vehicle wheel etc. are mentioned as a specific example.
• the metallic paint composition of the present invention can be particularly suitably used for aluminum vehicle wheels.
• the powder primer used in the coating method of the present invention those generally used in the metallic paint field can be used without particular limitation. Specific examples include trade name: V-PET # 5200 (manufactured by Dainippon Paint Co., Ltd.).
• the powder primer can be applied to the substrate by using a general powder primer coating method.
• the coating thickness of the powder primer is not particularly limited, but is, for example, 10 to 150 ⁇ m, preferably 30 to 120 ⁇ m, more preferably 50 to 100 ⁇ m.
• the metallic coating composition can be applied onto the substrate coated with the powder primer by using a general metallic coating method such as spray coating or bell coating.
• a general metallic coating method such as spray coating or bell coating.
• the process (B) (baking process) of heat-drying the painted metallic coating composition is unnecessary in principle, you may perform as needed.
• the coating film thickness of the metallic coating composition is not particularly limited, but is, for example, 1 to 20 ⁇ m, preferably 5 to 15 ⁇ m, more preferably 9 to 12 ⁇ m.
• the clear paint used in the coating method of the present invention can be used without particular limitation.
• a specific example is a clear paint for automobiles.
• Application of the clear paint onto the coating film of the metallic paint composition and heat drying can be performed by using a general clear paint application and heat drying method.
• the coating thickness of the clear coating is not particularly limited, but is, for example, 10 to 40 ⁇ m, preferably 15 to 30 ⁇ m, more preferably 20 to 25 ⁇ m.
• coated body of the present invention has a coating film of a powder primer on a substrate, and the coating film of the powder primer. It has the coating film of the metallic coating composition of the present invention, and further has the coating film of the clear coating as the outermost layer on the coating film of the metallic coating composition.
• Thickness 0.2 ⁇ m, particle diameter (D10): 5 ⁇ m, particle diameter (D50): 14.2 ⁇ m, particle diameter ( D90): 45.7 ⁇ m, aspect ratio (D50 / thickness): 71, difference between D90 and D10: 40.7 ⁇ m)
• the obtained metallic coating composition was spray-coated (C) so as to have a dry film thickness of 3 ⁇ m, baked at 150 ° C. for 20 minutes (B), and then “T-639 # C890” (large) Nippon Paint Co., Ltd.) was spray-coated so that the dry film thickness was 25 ⁇ m (C). Finally, baking was performed at 150 ° C. for 20 minutes (B) to obtain an evaluation sample coated with the metallic coating composition.
• the coating method of each metallic paint composition is described in the “Coating process” column of Table 2. In Table 2, “2C1B” indicates the 2-coat 1-bake method, and “3C3B” indicates the 3-coat 3-bake method.
• Examples 1 to 4 (2C1B) maintained the same glitter feeling as Comparative Examples 3 to 4 (3C3B).
• Comparative Examples 3 to 4 correspond to conventional metallic coating compositions containing an aluminum pigment and a nitrocellulose-based resin in a solvent. Therefore, the metallic paint composition of the present invention maintained a glittering feeling equivalent to that of the metallic coating film of the prior art by the 2C1B method, which has fewer steps than the prior art (3C3B method).
• the 2C1B method which has fewer steps than the prior art (3C3B method)
• Gloss retention (%) Glossiness after irradiation / Glossiness before irradiation ⁇ 100 [Evaluation criteria] ⁇ : Gloss retention ⁇ 85% and color difference ⁇ 3 ⁇ : Results other than the above “ ⁇ ” was determined to have sufficient light resistance required for metallic paints. Therefore, Examples 1 to 4 had the light resistance required for metallic paints. On the other hand, Comparative Examples 3 to 4 containing a nitrocellulose resin that causes a decrease in color difference (yellowing) did not show sufficient light resistance.
• the present invention can be used in the paint field.

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• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Wood Science & Technology (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Paints Or Removers (AREA)
• Application Of Or Painting With Fluid Materials (AREA)
• Laminated Bodies (AREA)

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• 2016
  • 2016-12-14 JP JP2016241962A patent/JP6386521B2/ja active Active
• 2017
  • 2017-12-14 CN CN201780077447.0A patent/CN110072955B/zh active Active
  • 2017-12-14 WO PCT/JP2017/044855 patent/WO2018110635A1/ja active Application Filing
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