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WO2016047253A1 - Procédé de fabrication d'un pigments à base de paillettes de métal - Google Patents

Procédé de fabrication d'un pigments à base de paillettes de métal Download PDF

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Publication number
WO2016047253A1
WO2016047253A1 PCT/JP2015/070367 JP2015070367W WO2016047253A1 WO 2016047253 A1 WO2016047253 A1 WO 2016047253A1 JP 2015070367 W JP2015070367 W JP 2015070367W WO 2016047253 A1 WO2016047253 A1 WO 2016047253A1
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WIPO (PCT)
Prior art keywords
slurry
flakes
metal pigment
flaky metal
pigment
Prior art date
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PCT/JP2015/070367
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English (en)
Japanese (ja)
Inventor
中尾　貴之
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Toyo Aluminum KK
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Toyo Aluminum KK
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Publication of WO2016047253A1 publication Critical patent/WO2016047253A1/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/12—Making metallic powder or suspensions thereof using physical processes starting from gaseous material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/62—Metallic pigments or fillers
    • C09C1/64—Aluminium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations

Definitions

  • the present invention relates to a method for producing a flaky metal pigment.
  • flake-shaped metal pigments (hereinafter also referred to as “flake-shaped metal pigments”) have been used in paints, inks, and the like because they exhibit an excellent metallic feeling when a coating film is formed.
  • flaky metal pigments have heretofore been produced by the following ball mill method.
  • metal powder prepared metal powder, organic solvent, and grinding aids such as higher fatty acids as raw materials. Next, these are put into a cylindrical drum, and further media (balls) are put. Then, the metal powder is flaked by rotating the drum and applying a mechanical force to the metal powder in the drum.
  • Such a ball mill method is suitable for producing a powder having an average particle diameter of 10 ⁇ m or more and a maximum particle diameter exceeding 20 ⁇ m, and the produced powder is widely used in coating techniques such as spray coating and screen printing. Has been.
  • a vacuum vapor deposition method in which a thin metal vapor deposition film is formed on a plastic film and is crushed to produce a flaky metal pigment. According to this, compared with the flaky metal pigment obtained by the ball mill method, it is possible to produce a flaky metal pigment having a uniform thickness, a smooth and flat surface, and an excellent metallic tone.
  • Patent Document 1 an aluminum vapor deposition layer is formed by a vacuum vapor deposition method, and this is subjected to ultrasonic treatment in a solvent to perform peeling, miniaturization, and dispersion treatment. Discloses a method for producing an aluminum pigment having a desired particle size.
  • the ultrasonic treatment as described above requires a lot of time for crushing the metal deposited film to a desired particle size.
  • the particle size is desired to be fine or when the thickness of the metal deposition layer is large, the pulverization does not proceed and the desired particle size cannot be obtained. For this reason, the method of crushing a metal vapor deposition film
  • the present invention has been made in view of the above situation, and an object of the present invention is to provide a method for producing a flaky metal pigment more efficiently than in the past.
  • Patent Document 1 requires a long processing time until a desired aluminum pigment is obtained, and even if an attempt is made to obtain a fine flaky pigment. It has been found that it is difficult to make the metal pigment fine to the extent necessary.
  • the method for producing a flaky metal pigment according to one aspect of the present invention includes a step of preparing a slurry including a flake made of metal, and a step of finely pulverizing the flake by high-pressure jetting the slurry.
  • the step of miniaturizing includes a step of injecting the slurry from the injection unit into the reaction chamber at a pressure of 70 MPa or more, and a thin piece contained in the injected slurry is disposed in the reaction chamber. And a step of colliding with a hard body.
  • the step of miniaturizing is performed by causing the slurry to be injected into the reaction chamber from the injection unit at a pressure of 70 MPa or more, and by causing the slurry injected from the injection unit to collide with each other. And a step of causing the flakes contained in the slurry to collide with each other.
  • the flakes are made of aluminum obtained by a vacuum deposition method.
  • a flaky metal pigment can be produced efficiently.
  • the flaky metal pigment according to this embodiment is produced by the method for producing a flaky metal pigment according to this embodiment, which will be described later.
  • the particle diameter of the flaky metallic pigment is not particularly limited, but P50, which is a 50% cumulative frequency of the area equivalent circle diameter in the number distribution measured by the flow particle image analyzer, is preferably 10.0 ⁇ m or less.
  • the “area circle equivalent diameter” is the diameter of a circle corresponding to the projected area of the captured particle image, and “P50” is 50% in the cumulative distribution of the area circle equivalent diameter in the number distribution.
  • the particle size Unless otherwise specified in the present specification, “particle diameter” means the above “area circle equivalent diameter”.
  • P50 of the flaky metallic pigment is more preferably 5.0 ⁇ m or less, and further preferably 2.0 ⁇ m or less.
  • the lower limit of P50 is not particularly limited, but considering the production efficiency, it is preferably 0.100 ⁇ m or more, more preferably 0.500 ⁇ m or more, and further preferably 1.000 ⁇ m or more.
  • the flaky metal pigment is made of metal.
  • the metal is preferably a metal that exhibits an excellent metallic feeling in image formation, and examples thereof include aluminum, copper, iron, stainless steel, and nickel.
  • aluminum is preferred from the viewpoint of being able to exhibit an excellent metallic feeling and from the viewpoint of manufacturing cost.
  • “metallic feel” is a bright color tone such as metallic luster that is visually recognized.
  • the aluminum is not limited to metallic aluminum, but may be an aluminum alloy or a mixture thereof.
  • the aluminum alloy include an alloy composed of Al, which is a main metal, and at least one selected from silicon (Si), magnesium (Mg), and a transition metal.
  • the flaky metal pigment is preferably made of Al from the viewpoint that industrial production is possible at a low cost and a high metallic feeling is exhibited.
  • flow type particle image analyzer examples include trade names “FPIA-2100”, “FPIA-3000”, and “FPIA-3000S” manufactured by Sysmex Corporation.
  • P50 measured by the flow type particle image analyzer means a value measured under the following measurement conditions.
  • Pmax and “P10” described later also mean values measured under the same measurement conditions.
  • Imaging unit High magnification imaging unit Magnification: 40 times (eyepiece 20 times x objective lens 2 times) Measurement mode: HPF measurement mode Measurement time: about 2 minutes Measurement solvent: Ethanol Binarization threshold setting coefficient: 85% Dilution rate with solvent at the time of measurement: 2000 times sheath liquid: ethanol.
  • the flaky metal pigment of this embodiment tends to have a sharper particle size distribution than the flaky metal pigment produced by the conventional ball mill method and the aluminum pigment produced by the production method disclosed in Patent Document 1. .
  • Pmax which is the value of the maximum particle diameter of the equivalent area circle diameter in the number distribution measured by a flow particle image analyzer, is preferably 15 ⁇ m or less, and is 5 ⁇ m or less. More preferably, it is 3 ⁇ m or less. If the value of Pmax is 15 ⁇ m or less, high concealment can be exhibited. Moreover, since the particle size distribution becomes sharp, an excellent metallic feeling can be exhibited.
  • the average thickness t is not particularly limited, but it may be usually 100 nm or less. However, in order to proceed efficient crushing by the production method of the present invention, 50 nm or less is preferable, more preferably 30 nm, further preferably 5 nm to 25 nm, and particularly preferably 10 nm to 25 nm. .
  • the average thickness t can be measured as follows. That is, first, several drops of a flaky metal pigment diluted with acetone are dropped on a glass substrate and allowed to dry naturally. Next, 20 points of flaky metal pigments forcedly aligned on this glass substrate were extracted using an atomic force microscope (trade name: “Nanopics 1000”, manufactured by Seiko Instruments Inc.), and each thickness was determined by tapping mode. Measure. Then, among the measured thicknesses of 20 points, an average value of the remaining 14 point thicknesses excluding the thicknesses of each of the upper value and the lower value is obtained, and the average value is defined as an average thickness t.
  • the average thickness t is less than 5 nm, most of the light passes through the flaky metal pigment, which may cause a decrease in metallic feeling, a decrease in concealment, and the like.
  • the average thickness t exceeds 100 nm, the particle size distribution of the flaky metal pigment by the production method of the present embodiment tends to be broad, and as a result, the luminance may be lowered and the metallic feeling may be lowered.
  • a metallic composition containing such a flaky metal pigment is applied on a substrate, irregular reflection of light due to the overlap between the flaky metal pigments on the substrate becomes remarkable, and a good metallic feeling is hardly exhibited. Tend to be.
  • the thickness of the flaky metal pigment of the present embodiment is uniform.
  • a coating film having a homogeneous metallic feeling can be formed.
  • the flaky metal pigment has two surfaces facing each other so as to be substantially parallel to the thickness direction, and it is preferable that the surface is flat. Also in this case, a coating film having a more homogeneous metallic feeling can be formed.
  • the ratio of the average thickness t to P50, P50 / t is preferably 1 or more and 100 or less, It is more preferably 3 or more and 100 or less, and further preferably 10 or more and 50 or less.
  • the aspect ratio represented by P50 / t is less than 1, since the thickness tends to be larger than the particle size of the flaky metal pigment, when a metallic composition containing this is applied on a substrate, The irregular reflection of light due to the overlap between the flaky metal pigments on the substrate becomes remarkable, and it tends to be difficult to obtain a good metallic feeling.
  • the aspect ratio represented by P50 / t exceeds 100, the thickness of the flaky metal pigment tends to be very thin, so that the light passes through the flaky metal pigment, thereby concealing. Decrease may be caused.
  • Pmax / P10 which is a ratio of P10 which is a value of 10% cumulative frequency in the number distribution measured by the flow type particle image analyzer of flaky metallic pigment to Pmax (however, The unit of Pmax is the same as the unit of P10), is preferably 1 or more and 21 or less, more preferably 1 or more and 18 or less, and further preferably 2 or more and 15 or less.
  • the metallic composition of this embodiment is a metallic composition containing the above-mentioned flaky metal pigment.
  • the use of the metallic composition of the present embodiment is not particularly limited.
  • applications that require metallic feeling and high definition such as paints, inks, resin moldings, cosmetics, and wiring of electronic circuit components.
  • the metallic composition of the present embodiment can contain an optional component, for example, a resin, a solvent, a coloring pigment (for example, an inorganic pigment, an organic pigment, and the like) in addition to the flaky metal pigment.
  • a coloring pigment for example, an inorganic pigment, an organic pigment, and the like
  • dispersants such as surfactant
  • stabilizers such as antioxidant and a ultraviolet absorber
  • the resin examples include epoxy resin, polyester resin, acrylic resin, acrylic silicone resin, vinyl resin, silicon resin, polyamide resin, polyamideimide resin, fluorine resin, boil oil, chlorinated rubber, amino resin, phenol resin, polyisocyanate resin, Two or more types of combinations such as urea resin are preferably used.
  • the solvent examples include organic solvents such as alcohols, glycols, ketones, esters, ethers, aromatics and hydrocarbons, and water.
  • organic solvents such as alcohols, glycols, ketones, esters, ethers, aromatics and hydrocarbons
  • water when water is used, when the flaky metal pigment contains aluminum or is made of aluminum, the surface of the flaky metal pigment may be coated with an arbitrary film in order to suppress the reaction between water and aluminum. preferable.
  • examples of such a film include a film made of a metal oxide, a resin, or the like.
  • the blending amount of the flaky metal pigment in the metallic composition is not particularly limited.
  • the blending amount varies depending on the use, and is generally preferably in the range of 0.1% by mass to 80% by mass.
  • the blending amount is preferably 0.1% by mass to 30% by mass, and more preferably 0.5% by mass to 20% by mass. Is more preferably 0.5% by mass or more and 10% by mass or less.
  • the compounding amount exceeds 30% by mass, the metallic composition cannot be kept in a slurry state and becomes a paste, and it tends to be difficult to form a homogeneous image.
  • it is less than 0.5% by mass, it tends to be difficult to form an image having a sufficient density.
  • the material of the substrate to be applied is not particularly limited, and includes inorganic materials such as metals, ceramics, and glass, synthetic resins, paper, and various electronic substrates. Can be mentioned.
  • the metallic composition according to the second embodiment is used for inkjet, as a substrate, paper such as non-coated printing paper, coated paper, coated printing paper such as glossy paper, synthetic resin film, Examples thereof include synthetic resin moldings, substrates such as glass, metal, and piping, and fibers such as clothing.
  • the metallic composition described in detail above can be produced by a known production method. For example, after mixing the above-mentioned flaky metal pigment, a dispersant, and a solvent, a dispersion is prepared using a stirrer, ball mill, bead mill, ultrasonic wave, jet mill, or the like. Then, a metallic composition can be manufactured by adding surfactant, resin, and another additive to the prepared dispersion liquid, stirring.
  • the coated product of the present embodiment is a coated product to which the above-described metallic composition is applied.
  • a coated material means what applied the metallic composition to the apply
  • the coated product of the present embodiment since the above-described flaky metallic pigment is applied, the coated product has an excellent metallic feeling, and the coated object is sufficiently concealed by the flaky metallic pigment.
  • the thickness of the coating film provided in the coating material of the present embodiment is not particularly limited, and another underlayer may be provided under the coating film, and another coating layer may be provided on the coating film. You may prepare.
  • the illustration of the application target object of this embodiment is the same as the base
  • the method for producing a flaky metal pigment of the present embodiment is a method for producing a flaky metal pigment, and is suitable for producing the above-described flaky metal pigment. Specifically, referring to FIG. 1, a step of preparing a slurry containing a thin piece made of metal (slurry preparation step: step S11), and a step of finely pulverizing the thin piece by spraying the slurry with high pressure (step of miniaturization: step S12).
  • slurry preparation step: step S11 a step of finely pulverizing the thin piece by spraying the slurry with high pressure
  • step S12 step of miniaturization
  • a slurry containing aluminum flakes is prepared (step S ⁇ b> 11).
  • the prepared slurry includes an aluminum flake made of aluminum and a solvent.
  • FIG. 2A is a schematic side view showing an example of the shape of an aluminum flake (hereinafter referred to as “Al flake”)
  • FIG. 2B is a schematic plan view showing an example of the shape of an Al flake.
  • the thickness t 0 of the Al flakes 10 may be set based on the average thickness (t) of the flaky metal pigment to be finally obtained, and is, for example, 100 nm or less.
  • the thickness t 0 is preferably 50 nm or less, more preferably 30 nm or less, further preferably 5 nm or more and 25 nm or less, and particularly preferably 10 nm or more and 25 nm or less.
  • the Al flakes 10 can be efficiently miniaturized in the miniaturization step described later. Furthermore, when the average thickness t exceeds 100 nm, the mechanical strength of the prepared Al flakes 10 becomes high, so the time for the miniaturization process becomes long, and the productivity tends to decrease remarkably.
  • the particle diameter D50 of the Al flakes 10 is not particularly limited, but is preferably 1 ⁇ m or more and 50 ⁇ m or less.
  • the particle diameter D50 of the Al flakes 10 is 50 ⁇ m or less, clogging of the nozzle for miniaturization can be suppressed and the miniaturization can be efficiently performed in a short time.
  • the particle size D50 means a particle size having a cumulative degree of 50% in a volume cumulative particle size distribution measured by a laser diffraction method.
  • the Al flakes 10 as described above those manufactured by a ball mill method, a vacuum deposition method, or the like can be used.
  • a sheet-like base material or a sheet-like base material on which a peeling resin layer is formed is prepared.
  • a sheet-like substrate for example, a film made of PET (polyethylene terephthalate) or the like can be used.
  • a coating film made of polyvinyl alcohol or the like can be used.
  • the vapor deposition layer which consists of aluminum is formed in the surface of a sheet-like base material (The surface of the resin layer for peeling when the resin layer for peeling is formed) by the vacuum evaporation method.
  • a multi-layer structure may be formed by alternately laminating multiple release resin layers and vapor deposition layers.
  • the thickness t 0 of the Al flakes 10 can be easily adjusted to 5 nm or more and 25 nm or less.
  • the aluminum vapor deposition layer is peeled off at the boundary of the surface of the sheet-like substrate (the surface of the peeling resin layer when the peeling resin layer is formed), and the peeled aluminum vapor deposition layer is crushed, An Al flake 10 is obtained.
  • the aluminum vapor deposition layer is peeled off by immersing the sheet-like base material on which the aluminum vapor deposition layer is formed in a solvent in which the sheet-like base material or the resin layer for peeling is dissolved.
  • a method is mentioned.
  • a method is employed in which the aluminum vapor deposition layer is peeled from the sheet-like substrate by dissolving the peeling resin layer.
  • the peeled aluminum vapor deposition layer can be pulverized, for example, by ultrasonic treatment of the solvent.
  • the peeled aluminum vapor deposition layer can be crushed by crushing the peeled aluminum vapor deposition layer with a crusher or the like.
  • the PVD pigment generally means a flake made of a metal manufactured by using the vacuum deposition method as described above.
  • any of water, a hydrophilic organic solvent, and a hydrophobic organic solvent can be used.
  • an organic solvent is preferably used when the flaky metal pigment is made of aluminum.
  • hydrophilic organic solvents include ethylene glycol, methyl ethyl diglycol, ethylene glycol monobutyl ether (butyl cellosolve), diethylene glycol monobutyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether.
  • glycol solvents such as dipropylene glycol monomethyl ether and dipropylene glycol monoethyl ether, glycol acetate solvents such as propylene glycol monomethyl ether acetate and ethyl diglycol acetate, and alcohol solvents such as isopropyl alcohol.
  • hydrophobic organic solvent include aliphatic hydrocarbons such as mineral spirit, isoparaffin, normal paraffin, and petroleum benzine, and aromatic hydrocarbons such as xylene, toluene, and solvent naphtha.
  • the solid content in the slurry (that is, the content ratio of the Al flakes 10) is not particularly limited as long as it can be jetted in the miniaturization step described later.
  • the content of the Al flakes 10 with respect to the total weight of the slurry is preferably 1% by mass to 30% by mass, more preferably 1% by mass to 20% by mass, and more preferably 1% by mass to 10% by mass. More preferably, it is as follows. When the content exceeds 30% by mass, the slurry cannot be maintained in a paste state, and there is a tendency that injection from a miniaturization nozzle becomes difficult. Moreover, when it is less than 1 mass%, the efficiency of a refinement
  • the obtained Al flakes 10 are present in a solvent
  • the mixture of the Al flakes 10 and the solvent is in the form of a slurry, it can be used as it is in the micronization step described later.
  • a solvent is further added to this to adjust the solid content in the mixture to an appropriate range (viscosity).
  • viscosity can be used in the miniaturization step described later.
  • Commercially available Al flakes are often in the form of a slurry.
  • ⁇ Refining process> Referring to FIG. 1, after the above-described slurry preparation process, the prepared slurry is sprayed at a high pressure to refine Al flakes 10 (step S12). Thereby, the surface 10a and the surface 10b are divided and the Al flakes 10 are refined. Thereby, P50 which is 50% cumulative frequency of area equivalent circle diameter in number distribution can manufacture efficiently the flaky metal pigment of a desired particle diameter.
  • the method of refining Al flakes by high-pressure jetting is a method of crushing by applying pressure to the slurry, jetting it at high speed, and applying a physical force to the Al flakes 10 in the jetted slurry.
  • the flaky metal pigment refined in this step is compared with the Al flakes prepared in the slurry preparation step, the thicknesses of both are relatively approximate, but the particle sizes of both are greatly different.
  • Examples of the method for refining the Al flakes by high-pressure injection include the following methods (1) to (4).
  • the method (1) or (2) it is preferable to use the method (1) or (2) from the viewpoint that the efficiency of miniaturization is high and a flaky metal pigment having a desired particle diameter can be produced in a short time.
  • the method (1) is more preferable because the efficiency of miniaturization is higher than that of (2).
  • the method (1) will be specifically described with reference to FIGS. 3 and 4, and the method (2) will be specifically described with reference to FIGS. 5 and 6.
  • step S31 the slurry is injected into the reaction chamber 40 from the nozzle 41 as an injection unit under a pressure of 70 MPa or more (injection process).
  • the arrow in a figure has shown the injection direction of the slurry.
  • step S32 the Al flakes 10 contained in the injected slurry are collided with the hard body 42 arranged in the reaction chamber 40 (collision step). Thereby, the Al flakes 10 are miniaturized.
  • the refined slurry is taken out of the reaction chamber 40 from the discharge portion 43.
  • the pressure applied to the slurry during injection from the nozzle 41 is preferably 70 MPa or more and 250 MPa or less, and more preferably 100 MPa or more and 250 MPa or less.
  • the present inventor has confirmed that the Al flakes 10 can be efficiently miniaturized under such pressure conditions.
  • the diameter of the nozzle 41 is not particularly limited, but is preferably 0.1 mm to 0.5 mm, more preferably 0.1 mm to 0.30 mm, and still more preferably 0.1 mm to 0.15 mm.
  • the slurry can be ejected at a high speed, and clogging of the nozzle 41 can be sufficiently suppressed.
  • the material of the hard body 42 is not particularly limited as long as it has higher hardness than the Al flakes 10.
  • An example of such a material is ceramic such as SiN.
  • the slurry flow rate is preferably 10 L / hour or more and 200 L / hour or less, more preferably 40 L / hour or more and 150 L / hour or less.
  • the inventor has confirmed that the Al flakes 10 can be efficiently miniaturized at such a flow rate.
  • the slurry injected into the reaction chamber 40 can be returned to the nozzle 41 from a reflux port (not shown) and injected again. Therefore, when this step is performed using a predetermined amount of slurry, the slurry can be repeatedly collided with the hard body 42 by setting the injection time to be long and the slurry to be refluxed.
  • the total amount of slurry used in this step is not particularly limited, but when the total amount is 50 g or more and 500 g or less, the spraying time (treatment time) is preferably 0.05 hours or more and 50 hours or less, and preferably 1 hour or more and 20 hours or less. It is preferable that it is less than time. In this case, the balance between miniaturization and processing time is excellent.
  • the temperature of the slurry is preferably 5 ° C. or more and 250 ° C. or less, and preferably 5 ° C. or more and 150 ° C. or less.
  • the reason is as follows. That is, the temperature of the slurry tends to increase by spraying at a high pressure. If the temperature of the slurry rises excessively, there is a concern that the boiling point of the solvent, the spontaneous ignition temperature, etc. will be reached. On the other hand, by controlling this temperature to at least 250 ° C. or less, it is possible to select a wide range of solvents, so that evaporation of the solvent, ignition, and the like can be suppressed. In addition, since the solvent can exist stably in this step, the stability of the miniaturization treatment is improved.
  • step S51 the slurry is injected into the reaction chamber 60 from the two nozzles 61a and 61b as the injection section under a pressure of 70 MPa or more (injection process).
  • the number of nozzles is two, but the method (2) is not limited to this.
  • the arrows in the figure indicate the slurry injection direction.
  • step S52 the slurry ejected from the nozzles 61a and 61b is caused to collide with each other so that the Al flakes contained in each slurry are caused to collide with each other (collision step). Thereby, the Al flakes 10 are miniaturized.
  • the refined slurry is taken out of the reaction chamber 60 from the discharge part 62.
  • an apparatus capable of performing the above-described micronization process using high-pressure injection is “Genus PY” manufactured by Genus. ”,“ Starburst ”manufactured by Sugino Machine,“ Nanomizer ”manufactured by Nanomizer, and the like.
  • “Starburst” can be suitably used in the above methods (1), (2) and (4) by variously selecting the configuration of the reaction chamber used in the injection process, and “Genus PY”
  • the method (3) can be suitably used, and the “nanomizer” can be suitably used for the method (4).
  • a flaky metal pigment having a desired particle size can be efficiently obtained in a short time by carrying out the slurry preparation step and the refinement step. Can be manufactured.
  • the flaky metal pigment having such a particle size cannot be produced by a conventional production method.
  • the Pmax of the flaky metal pigment produced by the flaky metal pigment production method of the present embodiment can be set to 15.000 ⁇ m or less.
  • the Pmax / P10 of the flaky metal pigment (where Pmax and P10 are the same) can be 1 or more and 21 or less, and can be 1 or more and 18 or less. is there.
  • the particle size distribution of the obtained flaky metal pigment tends to be sharper than that produced by the conventional production method. For this reason, it can use suitably for the metallic printing by the inkjet as which high definition is calculated
  • Example 1 As the flaky metal pigment, the flaky aluminum pigment according to Example 1 was produced as follows. First, a commercially available PVD pigment was prepared. The characteristics of this PVD pigment were as follows.
  • the prepared slurry is injected at high pressure, and the method (1) (the slurry accelerated by pressurization is made to collide with the hard body. Then, the Al flakes in the slurry were made to collide with the hard body, whereby the Al flakes were refined by a method of refining the Al flakes (a refinement process).
  • the conditions in the miniaturization process were as follows.
  • a slurry sample A1 containing the refined flaky metal pigment was taken out from “Starburst Small Machine”.
  • the sample A1 taken out was a slurry composed of PMA and flaky aluminum pigment, and the solid content was 5% by mass.
  • Example 2 and Example 3 A sample A2 in the form of a slurry containing a flaky metal pigment was produced in the same manner as in Example 1 except that the spraying time in the miniaturization step was 0.3 hours in Example 2 and 0.15 hours in Example 3.
  • Example 2 and Sample A3 Example 3) were produced. In addition, both solid content of sample A2 and sample A3 was 5 mass%.
  • the obtained sample B1 was a slurry composed of PMA and flaky aluminum pigment, and the solid content was 5% by mass.
  • ⁇ Average thickness of flaky metal pigment The average thickness t of each flaky metal pigment (flaked aluminum pigment) contained in Samples A1 to A3 and Sample B1 is determined according to the above-described method using an atomic force microscope (trade name: “Nanopics 1000”, manufactured by Seiko Instruments Inc.). ).
  • Table 1 shows the measurement results and calculation results of samples A1 to A3 and sample B1.
  • the “treatment time” in Table 1 means the injection time in the miniaturization process in Examples 1 to 3, and the treatment time in ultrasonic treatment in Comparative Example 1.
  • Example 2 When comparing Example 2 and Comparative Example 1, both P50 values were comparable, but the processing time of Example 2 was much shorter. Thus, according to the manufacturing method of this embodiment, the flaky metal pigment of a desired particle diameter can be manufactured efficiently. Moreover, also in Example 1 and Example 3, the flaky metal pigment of a desired particle diameter is obtained in a short time.
  • Samples A1 to A3 and Sample B1 are used to produce evaluation metallic compositions A1 to A3 and evaluation metallic composition B1, and these are used to evaluate coating film characteristic evaluation films A1 to A3 and A film for characteristic evaluation B1 was produced. And the characteristic of both coating films was evaluated by the method mentioned later.
  • the metallic composition for evaluation and the film for characteristic evaluation of the coating film were produced as follows. First, the sample A1 obtained in Example 1 above was weighed so that the solid content of the flaky aluminum pigment was 1.0 part by mass, then diluted with 10 parts by mass of ethyl acetate, and further nitrified cotton lacquer (nitrification) A metallic composition for evaluation A1 was prepared by adding 4 parts by weight of a mixture containing 14% by weight of cotton and the balance being a solvent such as toluene, ethyl acetate and alcohol, and an additive component. Similarly, metallic compositions for evaluation A2, A3 and B1 were prepared using the samples A2, A3 and B1 obtained in Examples 2 and 3 and Comparative Example 1.
  • the metallic composition for evaluation A prepared above was applied to a PET film (using a # 8 bar coater, Wet thickness: about 18.3 ⁇ m, speed 7), and then naturally dried in air at room temperature (25 ° C.) for 1 hour to produce a film A1 for evaluating coating film characteristics.
  • evaluation films A2, A3 and B1 were produced using the evaluation metallic compositions A2, A3 and B1 prepared above. The obtained evaluation films A1 to A3 and evaluation film B1 had a metallic feeling.
  • the visible light transmittances of the produced evaluation films A1 to A3 and evaluation film B1 were measured.
  • the visible light transmittance was measured using a transmittance measuring device (trade name: “Z-1001DP”, manufactured by Nippon Denshoku Industries Co., Ltd.).
  • the visible light transmittance indicates that the smaller the numerical value, the less the light is transmitted, that is, the higher the hiding power.
  • Each transmittance was calculated by comparing the transmittance of the PET film before forming the coating film as 100%.
  • evaluation of concealment 2 The hiding power of the produced evaluation films A1 to A3 and evaluation film B1 was visually observed. Specifically, using an upright stand type artificial solar illuminating lamp (manufactured by Celic Corporation, main unit XC-100 type, stand type ST-1500C), the light transmittance (hiding power) of the coated film is visually determined to be 10 Rated by stage. 0 indicates an uncoated PET film, and 10 indicates a state where light is completely blocked.
  • Table 2 shows the results of evaluation 1 and evaluation 2 of each concealment property.
  • Example 2 and Comparative Example 1 are compared with each other, although both have the same P50 flaky metallic pigment, in Concealing Evaluation 1, Example 2 has the same P50.
  • the transmittance was lower or comparable to that of Comparative Example 1 using the flaky metal pigment, and it was found that the hiding power of Example 2 was higher in the hiding property evaluation 2. Therefore, it turned out that the flaky aluminum pigment of Example 2 can exhibit high concealment property as compared with Comparative Example 1.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Powder Metallurgy (AREA)

Abstract

Cette invention concerne un procédé permettant de produire des pigments à base de paillettes de métal de manière plus efficace que par les techniques classiques. Ledit procédé de production d'un pigment à base de paillettes de métal comprend les étapes consistant à préparer une suspension épaisse contenant des paillettes de métal et microniser les paillettes par injection à haute pression de la suspension épaisse.
PCT/JP2015/070367 2014-09-25 2015-07-16 Procédé de fabrication d'un pigments à base de paillettes de métal Ceased WO2016047253A1 (fr)

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JP2014194961A JP2016065285A (ja) 2014-09-25 2014-09-25 フレーク状金属顔料の製造方法
JP2014-194961 2014-09-25

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000080409A (ja) * 1998-08-31 2000-03-21 Mitsui Mining & Smelting Co Ltd 扁平状微小銅粉及びその製造方法
JP2011246718A (ja) * 2011-06-28 2011-12-08 Oike Ind Co Ltd 鱗片状薄膜微粉末分散液
JP2013023562A (ja) * 2011-07-20 2013-02-04 Toyo Aluminium Kk アルミニウム顔料

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000080409A (ja) * 1998-08-31 2000-03-21 Mitsui Mining & Smelting Co Ltd 扁平状微小銅粉及びその製造方法
JP2011246718A (ja) * 2011-06-28 2011-12-08 Oike Ind Co Ltd 鱗片状薄膜微粉末分散液
JP2013023562A (ja) * 2011-07-20 2013-02-04 Toyo Aluminium Kk アルミニウム顔料

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