WO2023063056A1 - Particules de type tartre de développement de couleur de perle, encre et film de revêtement - Google Patents

Particules de type tartre de développement de couleur de perle, encre et film de revêtement Download PDF

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Publication number
WO2023063056A1
WO2023063056A1 PCT/JP2022/035555 JP2022035555W WO2023063056A1 WO 2023063056 A1 WO2023063056 A1 WO 2023063056A1 JP 2022035555 W JP2022035555 W JP 2022035555W WO 2023063056 A1 WO2023063056 A1 WO 2023063056A1
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layer
zinc sulfide
pearl
average thickness
particles
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PCT/JP2022/035555
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English (en)
Japanese (ja)
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明 富田
咲良 渡邉
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尾池工業株式会社
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Publication of WO2023063056A1 publication Critical patent/WO2023063056A1/fr

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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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • 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
    • C09C1/04—Compounds of zinc
    • 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
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • 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
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds

Definitions

  • the present invention relates to pearl-colored scaly particles, inks, and coating films.
  • various light interference pearl pigments have been used in fields such as paints, plastics, printing inks, and cosmetics.
  • the pearl pigments those obtained by coating the surface of scale-like powder as a base material with titanium oxide, iron oxide, or the like are known.
  • Patent Document 1 discloses that optically variable flakes having a three-layer structure of ZnS/MgF 2 /ZnS exhibit pearl coloration (paragraph [0010], see Table 1). Further, Patent Document 1 discloses that the total average thickness of the three layers of ZnS/MgF 2 /ZnS is 0.5 ⁇ m (500 nm) or less, and that the average particle size of the flakes is within the range of 2 ⁇ m to 20 ⁇ m. (see paragraph [0037]). Furthermore, Patent Literature 1 discloses that a vapor deposition method and a sputtering method are used as a method for forming a three-layer structure of ZnS/MgF 2 /ZnS (see paragraph [0024]).
  • Patent Document 1 the ZnS/MgF 2 /ZnS three-layer structure flakes of Patent Document 1 are mainly used for anti-counterfeiting cards, and ink can be applied by a bar coat printing method, a screen printing method, or the like. (see paragraph [0037]) and is not used for inkjet printing.
  • ink containing flakes having an average particle size of 2 ⁇ m to 20 ⁇ m as in Patent Document 1 is used for inkjet printing, ejection stability is extremely poor due to the size of the nozzle diameter of the inkjet printer head and the dispersion stability.
  • the flake consisting of three layers of ZnS/MgF 2 /ZnS in Patent Document 1 is described as having a total average thickness of 0.5 ⁇ m (500 nm) or less. There is no description of the average thickness, and no attempt is made to optimize the thickness of each of the three layers suitable for pearl coloring.
  • the object of the present invention is to solve the above-mentioned problems in the past and to achieve the following objects. That is, the present invention achieves excellent pearl color development by optimizing the thickness of each layer in a three-layer structure having a first zinc sulfide layer, a magnesium fluoride layer, and a second zinc sulfide layer in this order.
  • An object of the present invention is to provide pearl-colored scaly particles, an ink, and a coating film capable of achieving the desired effect.
  • Means for solving the above problems are as follows. Namely ⁇ 1> Having a first zinc sulfide layer, a magnesium fluoride layer, and a second zinc sulfide layer in this order, The average thickness of the first zinc sulfide layer is 30 nm or more, The average thickness of the magnesium fluoride layer is 25 nm or more, The second zinc sulfide layer has an average thickness of 30 nm or more, The pearl-colored scale-like particles are characterized in that the total average thickness of the first zinc sulfide layer, the magnesium fluoride layer and the second zinc sulfide layer is 330 nm or less.
  • the average thickness of the first zinc sulfide layer is 30 nm or more and 130 nm or less;
  • the average thickness of the magnesium fluoride layer is 25 nm or more and 60 nm or less,
  • ⁇ 4> The pearl-colored scale-like particles according to any one of ⁇ 1> to ⁇ 3>, which are for inkjet printing.
  • ⁇ 5> An ink containing the pearl-colored scale-like particles according to any one of ⁇ 1> to ⁇ 4>.
  • ⁇ 6> A coating film comprising the pearly-colored scaly particles according to any one of ⁇ 1> to ⁇ 4>.
  • FIG. 1 is a schematic diagram showing an example of the pearl-colored scale-like particles of the present invention.
  • FIG. 2 is a front view of the coating film of Configuration 1.
  • FIG. 3 is a view of the coating film of Configuration 1 viewed from an oblique direction.
  • FIG. 4 is a front view of the coating film of Configuration 2.
  • FIG. 5 is a front view of the coating film of Configuration 3.
  • FIG. 6 is a front view of the coating film of Configuration 4.
  • FIG. FIG. 7 is a diagram showing a method of measuring the absolute reflectance in the 5° specular direction and the absolute reflectance in the 45° specular direction in the deposited films of structures 1 to 4.
  • FIG. 8 is a graph showing the results of simulation and actual measurement of the 5° regular reflectance in the deposited film of structure 1.
  • FIG. FIG. 9 is a graph showing the results of simulation and actual measurement of the 5° specular reflectance in the deposited film of configuration 2.
  • FIG. 10 is a graph showing the results of simulation and actual measurement of the 5° specular reflectance in the deposited film of configuration 3.
  • FIG. 11 is a graph showing the results of simulation and actual measurement of the 5° regular reflectance in the deposited film of configuration 4.
  • FIG. FIG. 12 is a graph showing the results of simulation and actual measurement of the 45° specular reflectance in the deposited film of configuration 1;
  • FIG. 13 is a graph showing results of simulation and actual measurement of the 45° specular reflectance in the deposited film of configuration 2.
  • FIG. FIG. 14 is a graph showing the results of simulation and actual measurement of the 45° specular reflectance in the deposited film of configuration 3;
  • FIG. 15 is a graph showing the results of simulation and actual measurement of the 45° specular reflectance in the deposited film of structure 4.
  • FIG. 16 is a graph showing simulation results of 5° specular reflectance of Example 1, Example A, Example D, Example E, Comparative Example F, Comparative Example G, Comparative Example H, and Comparative Example I; be. 17 is a graph showing simulation results of 5° specular reflectance for Comparative Example A, Comparative Example B, Comparative Example C, Comparative Example D, and Comparative Example E.
  • FIG. 18 is a graph showing the relationship between the total average thickness of the first to third layers and the cumulative 50% volume particle diameter D50 after pulverization.
  • FIG. 19 is a schematic diagram showing a method of photographing the appearance of the coating film.
  • FIG. 20 is a diagram showing the appearance photographs of the coating films of Compositions 1 to 4, the coating films of Compositions 5 to 8, and the coating films of other companies.
  • FIG. 21 is cross-sectional SEM photographs of scaly particles obtained by pulverizing vapor deposition films of structures 1 to 4, scaly particles obtained by pulverizing vapor deposition films of structures 5 to 8, and a powder of another company.
  • FIG. 22 is an enlarged cross-sectional SEM photograph of scaly particles obtained by pulverizing the deposited film of structure 2.
  • FIG. FIG. 23 is an enlarged cross-sectional SEM photograph of scaly particles obtained by pulverizing the deposited film of structure 7.
  • FIG. FIG. 24 is an enlarged cross-sectional SEM photograph of the powder of another company's product (SXB).
  • FIG. 25 is SEM photographs of the particle shapes of the finely pulverized scaly particles of constitutions 1 to 4, the finely pulverized scaly particles of constitutions 5 to 8, and the products of other companies.
  • FIG. 26 is a diagram showing the particle size distribution of finely pulverized scale-like particles of configurations 1 to 4.
  • FIG. 27 is a diagram showing the particle size distribution of finely pulverized scaly particles of constitutions 5 to 8 and particles of another company's product.
  • FIG. 28 is a diagram showing the 5° specular reflection spectrum of each coating film of structures 1 to 4.
  • FIG. FIG. 29 is a diagram showing the 45° specular reflection spectrum of each coating film of structures 1 to 4.
  • the pearl-colored scaly particles of the present invention have a first zinc sulfide layer, a magnesium fluoride layer, and a second zinc sulfide layer in this order, and the first zinc sulfide layer has an average thickness of 30 nm or more. wherein the average thickness of the magnesium fluoride layer is 25 nm or more, the average thickness of the second zinc sulfide layer is 30 nm or more, and the first zinc sulfide layer, the magnesium fluoride layer and the second The total average thickness of the zinc sulfide layer and the three layers is 330 nm or less.
  • pearl pigments for example, flakes obtained by coating the surface of mica or glass flakes with a metal oxide (such as TiO 2 ), or a three-layer structure of TiO 2 /SiO 2 /TiO 2 (high refractive index layer/low scaly particles of refractive index layer/high refractive index layer).
  • a metal oxide such as TiO 2
  • TiO2 titanium oxide
  • the flakes obtained by coating the surface of the mica or glass flakes with a metal oxide have a seamless feel and feel like scaly particles obtained by finely pulverizing a vapor-deposited film having a three-layer structure of ZnS/MgF 2 /ZnS.
  • a moist feeling cannot be realized.
  • the ZnS/MgF 2 /ZnS 3-layer structure scaly particles of the present invention are superior to the conventional TiO 2 /SiO 2 /TiO 2 3-layer structure scaly particles in pearl color development. This is because the TiO 2 /SiO 2 /TiO 2 crystal structure of the deposited film obtained in the case of vapor deposition is an amorphous structure, so the refractive index is lower than that of the bulk. On the other hand, since ZnS/MgF 2 /ZnS has a crystal structure, the refractive index is close to the literature value, so the difference in refractive index is large, the reflectance is high, and the pearl color development is good.
  • the average By optimizing the thickness, it is possible to achieve scale-like particles exhibiting good pearl color development within the visible light wavelength range.
  • the pearl-colored scale-like particles 10 of the present invention are obtained by laminating a first zinc sulfide layer 1, a magnesium fluoride layer 2, and a second zinc sulfide layer 3 in this order. It has a three-layer structure, and the average thickness of each layer is designed to improve pearl color development, and it is pulverized to a cumulative 50% volume particle diameter D50 suitable for inkjet printing.
  • the content of zinc sulfide (ZnS) in the first and second zinc sulfide layers is preferably 98% by mass or more, more preferably 99% by mass or more, and even more preferably 99.9% by mass or more.
  • the content of zinc sulfide in the first and second zinc sulfide layers can be measured, for example, by X-ray fluorescence analysis (XRF).
  • the average thickness of the first zinc sulfide layer is 30 nm or more, preferably 30 nm or more and 130 nm or less, and more preferably 30 nm or more and 120 nm or less.
  • the average thickness of the second zinc sulfide layer is 30 nm or more, preferably 30 nm or more and 190 nm or less, and more preferably 30 nm or more and 170 nm or less.
  • the average thickness of the first and second zinc sulfide layers is, for example, when manufactured by a physical vapor deposition method, the thickness at 5 to 10 locations for the first and second zinc sulfide layers. It is the same as the average deposition thickness measured and averaged.
  • Examples of methods for measuring the average thickness of the first and second zinc sulfide layers include scanning electron microscope (SEM) observation, X-ray fluorescence analysis (XRF), and ultraviolet-visible spectroscopy.
  • SEM scanning electron microscope
  • XRF X-ray fluorescence analysis
  • ultraviolet-visible spectroscopy ultraviolet-visible spectroscopy.
  • the thicknesses of the first and second zinc sulfide layers are measured at 5 to 10 locations, and the average vapor deposition thickness can be used as the average thickness.
  • the average thickness is obtained by the X-ray fluorescence analysis (XRF)
  • the thicknesses of the first and second zinc sulfide layers are measured at 5 to 10 points by quantitative analysis, and the average value is taken as the average thickness. be able to.
  • the content of magnesium fluoride (MgF 2 ) in the magnesium fluoride layer is preferably 98% by mass or more, more preferably 99% by mass or more, and even more preferably 99.9% by mass or more.
  • the content of magnesium fluoride in the magnesium fluoride layer can be measured, for example, by X-ray fluorescence analysis (XRF).
  • the average thickness of the magnesium fluoride layer is 25 nm or more, preferably 25 nm or more and 60 nm or less, and more preferably 35 nm or more and 50 nm or less.
  • the total average thickness of the three layers of the first zinc sulfide layer, the magnesium fluoride layer and the second zinc sulfide layer is 330 nm or less, preferably 130 nm or more and 290 nm or less.
  • the pearl coloring particles of the present invention having the magnesium fluoride layer between the first zinc sulfide layer and the second zinc sulfide layer are scaly particles, flaky particles, tabular particles, and flake-like particles. And so on.
  • the scale-like particles mean particles having a substantially flat surface and having a substantially uniform thickness in the direction perpendicular to the substantially flat surface.
  • the shape of the substantially flat surface is not particularly limited and can be appropriately selected according to the purpose. Polygons such as polygons, substantially octagons, and random irregular shapes are included.
  • the cumulative 50% volume particle diameter D50 of the pearl-colored scaly particles is preferably 1.8 ⁇ m or less, more preferably 0.8 ⁇ m or more and 1.8 ⁇ m or less, still more preferably 0.7 ⁇ m or more and 1.7 ⁇ m or less, and 0.5 ⁇ m. More than 1.6 ⁇ m or less is particularly preferable.
  • the cumulative 50% volume particle diameter D50 is a particle size corresponding to 50% of the cumulative volume distribution of the particle size distribution curve obtained by laser diffraction, and the non-spherical scale particles are assumed to be complete spheres.
  • the D50 is a value different from the actual length in the long side direction (major diameter) and the length in the short side direction (minor diameter) of the scale-like particles.
  • means using the laser diffraction method include a laser diffraction/scattering particle size distribution analyzer.
  • the ratio of the scaly particles (cumulative 50% volume particle diameter D 50 (nm)/total average thickness of three layers (nm)) is preferably 5 or more, more preferably 10 or more.
  • the ratio of "D 50 (nm) / total average thickness of three layers (nm)" in the present invention is D 50 measured using a laser diffraction method, scanning electron microscope (SEM) observation, or fluorescence X It is a ratio calculated by dividing by the average thickness obtained from line analysis. Therefore, the ratio of "D 50 (nm)/average thickness (nm)" is different from the parameter generally called aspect ratio.
  • the method for producing pearl-colored scaly particles of the present invention includes forming a release layer on a substrate, forming a first zinc sulfide layer on the release layer by a vapor phase method, and forming the first zinc sulfide layer on the first zinc sulfide layer.
  • a magnesium fluoride layer is formed on the magnesium fluoride layer by a vapor phase method
  • a second zinc sulfide layer is formed on the magnesium fluoride layer by a vapor phase method to obtain a laminate
  • the laminate is peeled off from the base material. and pulverize the laminate.
  • pearl-colored scale-like particles 10 as shown in FIG. 1 can be produced efficiently.
  • the method for producing pearl-colored scaly particles of the present invention includes a peeling layer forming step, a first zinc sulfide layer forming step, a magnesium fluoride layer forming step, and a second zinc sulfide layer forming step. , a peeling process, a pulverizing process, and other processes as necessary.
  • the release layer forming step is a step of providing the release layer on the substrate.
  • the substrate is not particularly limited as long as it has a smooth surface, and various substrates can be used.
  • resin films, metals, and composite films of metals and resin films having flexibility, heat resistance, solvent resistance, and dimensional stability can be appropriately used.
  • the resin film include polyester film, polyethylene film, polypropylene film, polystyrene film, and polyimide film.
  • the metal include copper foil, aluminum foil, nickel foil, iron foil, and alloy foil.
  • Examples of the composite film of the metal and the resin film include those obtained by laminating the resin film and the metal.
  • the peeling layer various organic substances and solvents such as water that can be dissolved in the later peeling process can be used. Further, if the organic material constituting the peeling layer is appropriately selected, the organic matter adhered or remained on the magnesium fluoride layer or the first and second zinc sulfide layers functions as a protective layer for the scale-like particles. It is preferable because it can be The protective layer has a function of suppressing aggregation, oxidation, elution into a solvent, etc. of the scale-like particles. In particular, it is preferable to use the organic material used for the peeling layer as the protective layer, because it eliminates the need for a separate surface treatment step.
  • Examples of the organic material constituting the release layer that can be used as the protective layer include cellulose acetate butyrate (CAB), other cellulose derivatives, polyvinyl alcohol, polyvinyl butyral, polyethylene glycol, polyacrylic acid, polyacrylamide, and acrylic. Examples include acid copolymers and modified nylon resins. These may be used individually by 1 type, and may use 2 or more types together. Among these, cellulose acetate butyrate (CAB) is preferable from the viewpoint of high function as the protective layer.
  • CAB cellulose acetate butyrate
  • the method for forming the release layer is not particularly limited and can be appropriately selected depending on the intended purpose. , knife coating method, air knife coating method, comma coating method, U comma coating method, AKKU coating method, smoothing coating method, micro gravure coating method, reverse roll coating method, 4 roll coating method, 5 roll coating method, dip coating method, curtain coating method, slide coating method, die coating method, and the like. These may be used individually by 1 type, and may use 2 or more types together.
  • the first zinc sulfide layer forming step is a step of forming a first zinc sulfide layer on the release layer by a vapor phase method.
  • Examples of the vapor phase method include a vapor deposition method and a sputtering method, which are collectively referred to as physical vapor deposition (PVD).
  • PVD physical vapor deposition
  • the magnesium fluoride layer forming step is a step of forming a magnesium fluoride layer on the first zinc sulfide layer by a vapor phase method.
  • Examples of the vapor phase method include a vapor deposition method and a sputtering method, which are collectively referred to as physical vapor deposition (PVD).
  • PVD physical vapor deposition
  • the second zinc sulfide layer forming step is a step of forming a second zinc sulfide layer on the magnesium fluoride layer by a vapor phase method. As described above, a laminate is formed in which the first zinc sulfide layer, the magnesium fluoride layer, and the second zinc sulfide layer are laminated in this order on the release layer of the substrate.
  • Examples of the vapor phase method include a vapor deposition method and a sputtering method, which are collectively referred to as physical vapor deposition (PVD).
  • PVD physical vapor deposition
  • the peeling step is a step of peeling the laminate by dissolving the peeling layer.
  • the solvent capable of dissolving the peeling layer is not particularly limited as long as it is capable of dissolving the peeling layer, and can be appropriately selected according to the purpose.
  • the solvent capable of dissolving the release layer is not particularly limited and can be appropriately selected depending on the intended purpose.
  • the pulverizing step is a step of pulverizing the laminate separated from the substrate in the peeling step. By carrying out this pulverization step, the pearl-colored scale-like particles of the present invention are obtained.
  • the method used in the pulverization step is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include jet mills, ball mills, bead mills, vibration mills, and ultrasonic homogenizers. Furthermore, if necessary, various treatments may be carried out for recovery of the pearl-colored scaly particles and adjustment of physical properties. For example, the particle size of the pearl-colored scaly particles may be adjusted by classification, the scaly particles may be recovered by a method such as centrifugation or suction filtration, or the solid content concentration of the dispersion may be adjusted. good. Moreover, solvent substitution may be performed, and viscosity adjustment etc. may be performed using an additive.
  • Examples of the other steps include a step of taking out the pulverized pearl-colored scaly particles as a dispersion, and a step of recovering the scaly particles from the dispersion.
  • the dispersion liquid used in the present invention contains the pearl-colored scaly particles of the present invention, and preferably contains an organic solvent and water, and further contains other components as necessary.
  • the dispersion may be either water-based or solvent-based, but water-based is preferred from the standpoint of environmental friendliness.
  • the content of the pearl-colored scale-like particles is preferably 0.1% by mass or more and 50% by mass or less with respect to the total amount of the dispersion.
  • Organic solvent is not particularly limited and can be appropriately selected depending on the intended purpose. , amines, sulfur-containing compounds, and the like. These may be used individually by 1 type, and may use 2 or more types together.
  • polyhydric alcohols examples include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,3-butanediol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 2 ,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,3-hexanediol, 2,5-hexanediol, 1,5-hexanediol, glycerin, 1,2,6-hexanetriol, 2-ethyl-1,
  • polyhydric alcohol alkyl ethers examples include ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, and propylene glycol monoethyl ether. be done.
  • polyhydric alcohol aryl ethers examples include ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether.
  • nitrogen-containing heterocyclic compound examples include 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, ⁇ -caprolactam, ⁇ - butyrolactone and the like.
  • amides examples include formamide, N-methylformamide, N,N-dimethylformamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide and the like.
  • Examples of the amines include monoethanolamine, diethanolamine, and triethylamine.
  • Examples of the sulfur-containing compound include dimethylsulfoxide, sulfolane, thiodiethanol and the like.
  • the other components are not particularly limited and can be appropriately selected depending on the intended purpose. , antifoaming agents, viscosity modifiers, light stabilizers, weather stabilizers, heat stabilizers, antioxidants, leveling agents, antiseptic antifungal agents, rust inhibitors, pH adjusters and the like.
  • water for example, pure water such as ion-exchanged water, ultrafiltrated water, reverse osmosis water, distilled water, or ultrapure water can be used.
  • the ink of the present invention contains the pearl-colored scaly particles of the present invention, preferably contains a binder, and further contains other components as necessary.
  • the inks of the present invention may be either water-based or solvent-based.
  • the content of the pearl-colored scale-like particles is not particularly limited with respect to the total amount of the ink, and can be appropriately selected according to the purpose.
  • the ink of the present invention may contain a luster pigment other than the pearl color-developing scaly particles.
  • other bright pigments include metallic pigments (eg, aluminum pigments), pigments obtained from natural mica (eg, pearl pigments), glass flake pigments, and the like.
  • the binder is not particularly limited and can be appropriately selected depending on the intended purpose. resins, vinyl chloride resins, acrylic-styrene resins, acrylic-silicone resins, polyvinyl alcohol resins, polyether resins, alkyd resins, polyvinylpyrrolidone, cellulose, and the like. When the ink contains the binder, an ink having excellent fixability and dispersibility can be obtained.
  • the content of the binder is not particularly limited and can be appropriately selected depending on the purpose.
  • the same organic solvent and water as in the dispersion can be used.
  • the ink of the present invention can be applied, for example, by an inkjet method, a gravure coating method, a screen printing method, a spray coating method, a spin coating method, a blade coating method, a gravure offset coating method, a bar coating method, a roll coating method, a knife coating method, and an air knife coating method.
  • method comma coating method, U comma coating method, AKKU coating method, smoothing coating method, micro gravure coating method, reverse roll coating method, 4-roll coating method, 5-roll coating method, dip coating method, curtain coating method, slide It can be used for coating methods such as a coating method and a die coating method.
  • an inkjet method, a bar coating method, a spray coating method, a gravure coating method, and a screen printing method are preferable.
  • the coating film of the present invention contains the pearl-colored scaly particles of the present invention, preferably contains a binder, and further contains other components as necessary.
  • the coating film may be used as a coating film alone, or may be a coated product formed by the above-described coating method using the ink of the present invention on a substrate.
  • the substrate is not particularly limited and can be appropriately selected depending on the intended purpose. Window glass and films for buildings, agricultural films, and the like.
  • the pearly-colored scaly particles of the present invention can achieve excellent pearly coloration, they can be used in a wide variety of fields, such as paints, plastics, printing, foods, cosmetics, and automobiles. .
  • a first zinc sulfide layer having an average thickness of 40 nm was formed by depositing zinc sulfide on the release layer by a vacuum deposition method.
  • the average thickness of the first zinc sulfide layer is an average value obtained by measuring the thickness of the first zinc sulfide layer at five locations by quantitative analysis using X-ray fluorescence analysis (XRF).
  • XRF X-ray fluorescence analysis
  • a film of magnesium fluoride was formed on the first zinc sulfide layer by a vacuum deposition method to form a magnesium fluoride layer with an average thickness of 50 nm.
  • a second zinc sulfide layer having an average thickness of 40 nm was formed on the magnesium fluoride layer by the same method as the first zinc sulfide layer.
  • a vapor deposition film of configuration 1 was obtained in which the release layer, the first zinc sulfide, the magnesium fluoride layer and the second zinc sulfide layer were laminated in this order on the PET film.
  • Vapor-deposited films of Structures 2 to 4 were also produced in the same manner as described above.
  • Each vapor-deposited film was finely pulverized (pulverized as finely as possible) for inkjet printing to make the cumulative 50% volume particle diameter D50 1.8 ⁇ m or less to obtain pearl-colored scale-like particles of constitutions 1 to 4.
  • butyl acetate was sprayed onto the PET film surface on which the vapor deposition film was formed to dissolve the release layer, and the vapor deposition film was scraped off with a doctor blade.
  • the mixture of the obtained deposited film and butyl acetate was subjected to a fine pulverization process until the target cumulative 50% volume particle size D50 was 1.8 ⁇ m or less. .
  • Pearl coloring inks of constitutions 1 to 4 were prepared by dispersing the above pearl coloring scaly particles in butyl acetate. (5) A polyethylene terephthalate (PET) film (transparent) was coated with pearl colored inks of constitutions 1 to 4 using a bar coater. (6) A black tape was attached to half of the PET film on the side opposite to the ink-coated surface, and the coating films of Structures 1 to 4 were visually observed and various data measurements were performed.
  • PET polyethylene terephthalate
  • a black tape was attached to half of the PET film on the side opposite to the ink-coated surface, and the coating films of Structures 1 to 4 were visually observed and various data measurements were performed.
  • FIG. 2 is a front view of the coating film of Configuration 1.
  • FIG. 3 is a view of the coating film of structure 1 viewed from an oblique direction.
  • FIGS. 2 and 3 when the vision is changed from the front direction to the oblique direction, it is recognized that the peak wavelength of the pearl-colored reflected light shifts and the color changes.
  • FIG. 4 is a front view of the coating film of composition 2, and the left side is a coating obtained by applying a pearl-colored ink with a high solid content concentration of pearl-colored scaly particles in the pearl-colored ink with a bar coater. membrane.
  • FIG. 5 is a front view of the coating film of composition 3, and the left side is a coating obtained by applying a pearl-colored ink with a high solid content concentration of pearl-colored scaly particles in the pearl-colored ink with a bar coater. membrane.
  • FIG. 6 is a front view of the coating film of composition 4, and the left side is a coating obtained by applying a pearl-colored ink with a high solid content concentration of pearl-colored scaly particles in the pearl-colored ink with a bar coater. membrane.
  • Example 1 to 4 Examples A to D, and Comparative Examples A to I
  • Example 1 ⁇ Setting the lower limit of the average thickness of each of the three layers by simulation (vapor deposition film)>
  • Example 1 Example A, Example D, Example E, Comparative Example F, Comparative Example G, Comparative Example H, and Comparative Example I, which were changed to the average thickness of each of the three layers shown in Table 2
  • visual color was evaluated, and the simulation results for 5° specular reflectance are shown in Table 2 and FIG.
  • Comparative Example A, Comparative Example B, Comparative Example C, Comparative Example D, and Comparative Example E which were changed to the average thickness of each of the three layers shown in Table 2
  • visual color was evaluated, and simulation of 5 ° regular reflectance was performed.
  • the results are shown in Table 2 and FIG.
  • Tables 3-1 to 3-3 show the simulation results of 5° specular reflection of Example 1 (structure 1), Example A (lower limit of structure 1), Example E, and Comparative Examples A to I. It was shown to. Criteria for determining the lower limit of the average thickness of each of the three layers in the blue region include satisfying the following (1) and (2).
  • (1) (Maximum value of reflectance at wavelength 380 nm to 530 nm)/(Minimum value of reflectance at wavelength 420 nm to 630 nm) is 3.0 or more
  • the minimum value of the reflectance is in the wavelength range of 420 nm to 630 nm.
  • Example 4 ⁇ Setting the upper limit of the average thickness of the total of three layers> An upper limit was set for the total average thickness of the three layers to pulverize each deposited film into a range of cumulative 50% volume particle diameter D50 that can be used for inkjet printing. The results are shown in FIG. 18, Tables 4 and 5.
  • the average thickness of each layer is an average value obtained by measuring the thickness of each layer at five locations by quantitative analysis using X-ray fluorescence spectroscopy (XRF).
  • FIG. 22 shows an enlarged cross-sectional SEM photograph of scaly particles obtained by pulverizing the deposited film of Structure 2.
  • FIG. 23 shows an enlarged cross-sectional SEM photograph of scaly particles obtained by pulverizing the deposited film of Structure 7.
  • FIG. 24 shows an enlarged cross-sectional SEM photograph of the powder of the competitor's product (SXB). From the results of FIGS. 21 to 24, it can be confirmed that ZnS/MgF 2 /ZnS and TiO 2 /SiO 2 /TiO 2 have a three-layer structure from the cross section. I understand.
  • FIG. 24 is an enlarged SEM photograph of the powder of another company's product, and the part where the coating layer (TiO 2 ) on the surface is partially peeled off and mica inside can be confirmed is photographed.
  • Other companies' products are coated with large-grained mica in a post-treatment, which basically results in a large-grained grain (there is no pulverization after coating).
  • the powders of configurations 1 to 8 obtained by pulverizing the three-layer vapor deposition films of ZnS/MgF 2 /ZnS and TiO 2 /SiO 2 /TiO 2 have a smaller particle size when the total thickness of the three layers is thinner. It can be seen that it is.
  • the obtained coating films of configurations 1 to 4 were measured using an ultraviolet-visible-near-infrared spectrophotometer (SolidSpec-3700, manufactured by Shimadzu Corporation) under the following measurement conditions at absolute reflections of 5° and 45°. were measured for L * , a * , b * , Y, x, and y.
  • the results are shown in Table 7.
  • [Measurement condition] ⁇ Lighting: D65 ⁇ Field of view: 2 degrees
  • the 5 ° specular reflection spectra of the coating films of configurations 1 to 4 measured with an ultraviolet-visible near-infrared spectrophotometer (SolidSpec-3700, manufactured by Shimadzu Corporation) are shown in FIG.
  • the 45° specular reflection spectrum of the coating film of No. 4 is shown in FIG.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

La présente invention concerne des particules de type tartre de développement de couleur de perle, dont chacune comprend séquentiellement une première couche de sulfure de zinc, une couche de fluorure de magnésium et une seconde couche de sulfure de zinc dans cet ordre; la première couche de sulfure de zinc ayant une épaisseur moyenne de 30 nm ou plus; la couche de fluorure de magnésium ayant une épaisseur moyenne de 25 nm ou plus; la seconde couche de sulfure de zinc ayant une épaisseur moyenne de 30 nm ou plus; et l'épaisseur totale moyenne des trois couches, à savoir la première couche de sulfure de zinc, la couche de fluorure de magnésium et la seconde couche de sulfure de zinc, étant de 330 nm ou moins.
PCT/JP2022/035555 2021-10-13 2022-09-15 Particules de type tartre de développement de couleur de perle, encre et film de revêtement WO2023063056A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02173162A (ja) * 1988-11-21 1990-07-04 Deposition Sciences Inc 顔料フレークの製造方法
JPH0858224A (ja) * 1994-08-23 1996-03-05 Toppan Printing Co Ltd 情報担持体
JPH101701A (ja) * 1996-06-10 1998-01-06 Nittetsu Mining Co Ltd 多層膜被覆粉体
JP2001271006A (ja) * 2000-03-24 2001-10-02 Nittetsu Mining Co Ltd 多層膜被覆粉体およびその製造方法
JP2005528503A (ja) * 2002-05-31 2005-09-22 ジェイディーエス　ユニフェイズ　コーポレーション 全誘電性光回折顔料
KR100853696B1 (ko) * 2007-04-23 2008-08-25 충북대학교 산학협력단 다중색상의 진주안료 및 그 제조방법
JP2013502467A (ja) * 2009-08-19 2013-01-24 エッカルト ゲゼルシャフト ミット ベシュレンクテル ハフツング 非銀色の干渉色および狭いサイズ分布を有する高光沢多層効果顔料、およびそれを製造するための方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02173162A (ja) * 1988-11-21 1990-07-04 Deposition Sciences Inc 顔料フレークの製造方法
JPH0858224A (ja) * 1994-08-23 1996-03-05 Toppan Printing Co Ltd 情報担持体
JPH101701A (ja) * 1996-06-10 1998-01-06 Nittetsu Mining Co Ltd 多層膜被覆粉体
JP2001271006A (ja) * 2000-03-24 2001-10-02 Nittetsu Mining Co Ltd 多層膜被覆粉体およびその製造方法
JP2005528503A (ja) * 2002-05-31 2005-09-22 ジェイディーエス　ユニフェイズ　コーポレーション 全誘電性光回折顔料
KR100853696B1 (ko) * 2007-04-23 2008-08-25 충북대학교 산학협력단 다중색상의 진주안료 및 그 제조방법
JP2013502467A (ja) * 2009-08-19 2013-01-24 エッカルト ゲゼルシャフト ミット ベシュレンクテル ハフツング 非銀色の干渉色および狭いサイズ分布を有する高光沢多層効果顔料、およびそれを製造するための方法

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