WO2003076526A1 - Poudre enrobee, composition de revetement et articles revetus - Google Patents
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- WO2003076526A1 WO2003076526A1 PCT/JP2002/002434 JP0202434W WO03076526A1 WO 2003076526 A1 WO2003076526 A1 WO 2003076526A1 JP 0202434 W JP0202434 W JP 0202434W WO 03076526 A1 WO03076526 A1 WO 03076526A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
- C09C1/0024—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a stack of coating layers with alternating high and low refractive indices, wherein the first coating layer on the core surface has the high refractive index
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
- C09C1/0051—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a stack of coating layers with alternating low and high refractive indices, wherein the first coating layer on the core surface has the low refractive index
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09C1/642—Aluminium treated with inorganic compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09C3/06—Treatment with inorganic compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09C3/06—Treatment with inorganic compounds
- C09C3/063—Coating
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/36—Pearl essence, e.g. coatings containing platelet-like pigments for pearl lustre
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- 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
- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/10—Interference pigments characterized by the core material
- C09C2200/1054—Interference pigments characterized by the core material the core consisting of a metal
-
- 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
- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/24—Interference pigments comprising a metallic reflector or absorber layer, which is not adjacent to the core
-
- 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
- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
- C09C2200/302—Thickness of a layer with high refractive material
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
- C09C2200/303—Thickness of a layer with low refractive material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
Definitions
- the present invention relates to a film-coated powder, a coating composition, and a coated material, and in particular, can exhibit a vivid, beautiful glowing powder, and a color shift (color change depending on a viewing angle).
- the present invention relates to a coating composition for automatic light vehicle coating, general coating, color paint coating, color ink, toner, and the like, and a coated product thereof.
- TECHNICAL FIELD The present invention relates to a multilayer film-coated powder and a method for producing the same, and more particularly to a method for controlling the coating of a light interference multilayer film on the surface of a base particle to be used for a color toner, a color ink, a paint or a pigment for cosmetics.
- the present invention relates to a magnetic powder and a method for producing the same.
- the present inventors have previously proposed a method of forming a metal film on substrate particles and whitening the powder by the reflection effect of the film (Japanese Patent Application Laid-Open Nos. 3-2713776 and 3-313). No. 274 278), the base particles are dispersed in a metal alkoxide solution, and the metal alkoxide is hydrolyzed to form a uniform metal oxide having a thickness of 0.01 to 20 m on the surface of the base particles.
- Japanese Patent Application Laid-Open No. 6-228604 invented a method of forming a powder film having a metal oxide film containing a metal different from the metal constituting the substrate. ).
- the powders provided with a plurality of metal oxide films or metal films mentioned above have a thickness of each layer.
- a special function can be provided by adjusting the thickness of the base particles.For example, coating films having different refractive indices are provided on the surface of the base particles at a thickness corresponding to a quarter wavelength of the incident light. Then, a powder that reflects all the incident light is obtained. When this is applied to a magnetic particle as a base particle, light can be reflected to produce a white toner powder. Further, each unit constituting the light interference multilayer film on the surface of the powder can be obtained. It was shown that when the film thickness is set so that the coating layer has a specific interference reflection peak of the same wavelength, a monochromatic powder can be obtained without using a dye or a pigment.
- the base material is a powder
- the base material is a powder
- the film thickness is designed without any correction
- the fitting after each layer coating may cause the reflectance value after the final layer coating to go away from the target value.
- each coating film is adjusted so that the maximum or minimum reflection wavelength measured by a spectrophotometer becomes a desired value considered when the base material is a flat body.
- the film is formed, there is also a problem that the multilayer-coated powder finally obtained does not have a desired reflection intensity at a desired wavelength.
- the thickness of each coating film is designed so that the reflection intensity of light of a specific wavelength is increased.
- the designed film thickness the desired reflection intensity is obtained at a desired wavelength.
- These pigments can be used in anti-counterfeiting secret documents such as banknotes, checks, check cards, credit cards, income stamps, stamps, railway and air tickets, telephone cards, lottery tickets, It is becoming increasingly important for gift vouchers, travel and identification cards.
- a printed matter using a printing ink prepared using the color shift effect pigment and a printed matter using a normal printing ink can be reliably distinguished by the naked eye, and can be easily distinguished.
- pigments having a color-shifting effect that exhibits an angle-dependent color change between two or more intense interference colors, and thus a noticeable color change.
- CVD Chemical Vapor Deposition
- Goniochroma chip clusters based on transparent silicate substrates or coated iron (III) oxide platelets are described in West German Patent (DE-A) 196 185695, European Patent (EP-). A) It is described respectively in the description of US Pat. No. 7,535,545 and in the earlier German Patent Application No. 1 98086 57.1.
- a raster pigment different from the prior art raster pigments, in a substrate material and in the form of a Z or coating coating, it is heated in a reducing atmosphere and A) colorless with a refractive index n ⁇ l.8 B) Novel goniochromatic raster pigments based on silicate platelets coated with titanium dioxide, consisting of at least one layer of packets with a colorless coating having a refractive index n ⁇ 2.0
- Goniochromaticlaster pigments Patent Publication of BASF Actchengezelshaft, Germany, JP 2000-44834.
- the raster pigment described in JP-A-2000-44834 only shows an angle-dependent color change from greenish blue to purple, and other pigments that change to a vivid color such as red or yellow are not described. At present there is not enough disclosure.
- a film-coated powder and a coating composition that have a high brightness, have a color shift effect showing an angle-dependent color change between strong interference colors, have advantageous application characteristics, and expand the range of coloring possibilities Objects and coatings have been sought.
- the present inventors have made the number of coating films larger than before and made it a multi-layer coated powder of at least two or more layers, and in film design, increased the reflectance at the wavelength of the maximum value of the reflection spectrum, By reducing the wavelength width of the reflection peak having the maximum value, a film-coated powder having a vivid color shift (color change) effect with improved lightness and chroma was obtained.
- the problems described above are that the incident angle of light on the powder is not constant like a flat plate, and that the optical path length in the film for each coated particle is not constant like a flat plate. Therefore, by performing a specific correction when designing the film thickness, the multilayer film-coated powder having the desired reflection intensity at a desired wavelength by having the designed film thickness is obtained. And a method for producing the same.
- the present invention relates to the following.
- the reflection spectrum has a wavelength between 380 and 780 nm.
- L> and the vertical axis reflectivity 100% height (specified reflectivity R) are displayed with L to R 5: 2, the peak height ( H) to half width (W)
- the coating film has at least two layers having different refractive indices
- Each film thickness of the coating film is
- the base particle is based on the multilayer film reflection intensity R flat in the case of a multilayer-coated flat plate that selects the material of the base particles, the number of coating layers, the coating order of each coating layer, the material of each coating layer, and the desired reflected light wavelength.
- the reflection intensity R ( ⁇ ) value of the multilayer-coated powder corrected by the shape and particle size of the multilayer has a maximum value or a minimum value at a desired wavelength.
- dj thickness of the j-th layer from the bottom
- Each of the selected coating layers is coated on the selected base particles by changing the film thickness in several steps in a stepwise manner to obtain a particle-coating film coating powder.
- measured film thickness value (d H) it also measures the respective membrane coated powder by a spectrophotometer
- the optical film thickness (nd) of each coating layer of the film coating powder for particle diameter correction was determined, and the actual film thickness value and refractive index (n) of each coating layer of the film coating powder for particle diameter correction were obtained.
- the ratio (nd / nd M ) of the optical film thickness (nd) of each coating layer to the product (nd M ) was calculated.
- a coating composition comprising the film-coated powder described in 1 above. 9. A coated material obtained by applying the coating composition described in 8 above.
- Multilayer coating powder having at least two coating layers having different refractive indices on the base particles and reflecting light of a specific wavelength, wherein each coating film has a thickness of:
- the base particle is based on the multilayer film reflection intensity R flat in the case of a multilayer-coated flat plate that selects the material of the base particles, the number of coating layers, the coating order of each coating layer, the material of each coating layer, and the desired reflected light wavelength.
- a multi-layer coated powder characterized in that the multi-layer coated powder has a film thickness such that the reflection intensity R ( ⁇ ) value of the multi-layer coated powder corrected by the shape and particle size becomes a maximum value or a minimum value at a desired wavelength.
- the following recurrence formula 1 is used to determine the multilayer film reflection intensity based on the material of the selected base particles, the number of coating layers, the coating order of each coating layer, the material of each coating layer and the desired reflected light wavelength.
- r Fresnel reflection coefficient at the interface between the j-th layer from the bottom and the layer directly above it
- Rj the amplitude reflection intensity between the first layer from the bottom j-th layer and the layer immediately above it
- the R ( ⁇ ) value is a film thickness at which a maximum value or a minimum value is obtained at a desired wavelength in consideration of shape correction.
- Each of the selected coating layers is coated on the selected base particles by changing the film thickness in several steps in a stepwise manner to obtain a particle-coating film coating powder.
- film thickness value of (d M) is measured, the optical film thickness of each coating layer of the film-coated powder of each was measured by a spectrophotometer their respective particle size correcting film-coated powder (nd ) And the ratio (nd M ) of the optical film thickness (nd) of each coating layer to the product (nd M ) of the actual film thickness value of each coating layer and the refractive index (n) of each film coating powder for particle size correction.
- / nd H
- ⁇ desired reflected light wavelength, nj refractive index of the j-th layer from the bottom,
- the actual film thickness value (d M ) of each coating layer of the particle-size-correcting film-coated powder is measured by cutting each of the particle-size-correcting film-coated powder and measuring the cut surface. 13.
- the base particle is based on the multilayer film reflection intensity R flat in the case of a multilayer-coated flat plate that selects the material of the base particles, the number of coating layers, the coating order of each coating layer, the material of each coating layer, and the desired reflected light wavelength.
- the film thickness of each coating layer is determined so that the reflection intensity R () value of the multilayer-coated powder corrected by the shape and particle size becomes the maximum value or the minimum value at the desired wavelength.
- the multilayer film reflection intensity R flat in the case of a multilayer film-coated flat plate in which the material of the base particles, the number of coating layers, the coating order of each coating layer, the material of each coating layer, and the desired reflected light wavelength are selected. Reflection intensity R of multi-layer coated powder corrected by substrate particle shape and particle size
- each coating layer is determined so that the ( ⁇ ) value becomes a maximum value or a minimum value at a desired wavelength, and the film is manufactured so as to have the determined film thickness value. Production method of multi-layer film coated powder.
- the following recurrence formula 1 is used to determine the multilayer film reflection intensity based on the material of the selected base particles, the number of coating layers, the coating order of each coating layer, the material of each coating layer and the desired reflected light wavelength. + Rj ex P ( -2i 3 ⁇ 4)
- Each of the coating layers selected on the selected base particles is coated in several steps with different thicknesses to obtain a film coating powder for particle size correction.
- Film thickness value
- r Fresnel reflection coefficient at the interface between the j-th layer from the bottom and the layer immediately above it
- Rj, ji the amplitude reflection intensity between the j-th layer from the bottom and the layer immediately above it
- the actual film thickness value (d M ) of each coating layer of the particle-size-correcting film-coated powder is measured by cutting each of the particle-size-correcting film-coated powder and measuring the cut surface.
- FIG. 1 is a diagram showing calculated values of the relative reflectance of each coating film obtained by Expressions 1 and 2 in Example 10;
- FIG. 2 shows a relationship curve (broken line) between the actual film thickness value (d M ) and the optical film thickness value (nd) of the first-layer SiO 2 film particle diameter correction film-coated powder in Example 10.
- FIG. 3 shows a relationship curve (broken line) between the actual film thickness value (d M ) and the optical film thickness value (nd) of the second-layer TiO 2 film diameter-correcting film-coated powder in Example 10.
- FIG. 4 is a diagram showing the calculated values of the relative reflectance of each coating film obtained by the correction according to the expressions 1 and 2 and the particle diameter in Example 10.
- FIG. 5 is a diagram showing the relative reflectance of each coating film of the multilayer coating powder actually manufactured in Example 10.
- FIG. 6 is a diagram showing a calculated value of a relative reflectance of each coating film obtained in Comparative Example 1 without performing correction by Expressions 1 and 2.
- FIG. 7 is a diagram showing the relative reflectance of each coating film of the multilayer coating powder actually manufactured in Comparative Example 1.
- the film-coated powder, the coating composition, and the coated material of the present invention have a reflection spectrum between 380 nm and 780 nm when the vertical reflection of the film-coated powder is measured on the surface of the base particles.
- the film-coated powder, the coating composition and the coated material of the present invention suppress the deposition of a solid phase that does not become a film by the following operations and actions, and have a uniform thickness on the surface of the base particles. It is presumed that the film of the above can be formed with a desired thickness.
- a buffer solution as the reaction solvent and adjust the pH to a certain level to make it acid or alkali. The effect of the heat is reduced and the erosion of the substrate surface is prevented;
- the ultrasonic dispersion not only improves the dispersibility of the base material particles, especially the magnetic substance such as magnetite powder, but also improves the diffusibility of the film component. In addition, it prevents adhesion between the films and improves the dispersibility of the coated substrate particles; 3 Precipitates the film components at an appropriate reaction speed and deposits a solid phase that does not become a film Suppress.
- the electric charge on the surface of the film-coated powder can be kept constant, and due to the function of the electric double layer, there is no aggregation of the film-coated powder and dispersed particles can be obtained.
- the pH varies depending on the combination of the substance of the substrate and the type of metal compound formed in the solution by the film forming reaction, and it is preferable to avoid the isoelectric point of both.
- the film-coating powder does not agglomerate or adhere to each other even when a magnetic substance is used as a base, even though a water-soluble raw material is used, and the preferable film thickness control is achieved.
- a film-coated powder that can be produced.
- a functional powder in which the characteristics (eg, magnetic characteristics) of the base particles are maintained at a high level.
- the film-coated powder, the coating composition, and the coated material of the present invention are based on a proprietary technique, and the number of films is preferably two or more to increase the film thickness, thereby increasing the reflection vector.
- the ratio (H / W) of the peak height (H) to the half-value width (W) is equal to or greater than the specific value described above. It has high saturation, has a beautiful glow, has a vivid color shift effect, has advantageous application characteristics, and is capable of expanding the range of coloring possibilities.
- the ratio (H / W) between the peak height (H) and the half-value width (W) is defined as 380 to 7 in the reflection spectrum when the vertical reflection of the film-coated powder is measured as described above. Displayed so that the ratio L: R between the 400 nm length ⁇ specified wavelength L> and the vertical axis reflection 100% height (specified reflectivity R) between 80 nm is 5: 2.
- the peak height ( It is necessary to maintain a spectrophotometric characteristic in which the ratio (H / W) of H) to the half width (W) is 1 or more, preferably 1.5 or more, and more preferably 2 or more. When the ratio (H / W) is less than 1, the width of the reflected color becomes wide, the color becomes pale, and the color does not become vivid.
- coating compositions are useful in many fields of industry, for example in automotive coatings, decorative coatings, plastic pigment coloring, paints, printing inks and the like.
- Such a film-coated powder, a coating composition and a coated material of the present invention can be used as a forgery-preventing secret document such as a banknote, a check, a check card, a credit card, a revenue stamp, a stamp, a railway and airline ticket, and a telephone card.
- a forgery-preventing secret document such as a banknote, a check, a check card, a credit card, a revenue stamp, a stamp, a railway and airline ticket, and a telephone card.
- a magnetic, conductive, or dielectric material is used as the base, additional effects such as moving force, rotation, movement, and heat generation will occur due to reactions caused by external factors such as electric and magnetic fields.
- a magnetic material when used as a base, it can be applied as a color magnetic toner or a color magnetic ink without impairing the magnetism.
- the coating film (substrate particles are coated)
- a special function can be provided by adjusting the thickness of each layer (layer of a film involved in light interference).
- alternate coating films having different refractive indices are formed on the surface of the base particles so that the refractive index n of the material forming the coating and an integer of 1/4 of the wavelength of visible light are satisfied so as to satisfy the following equation (3).
- a film having a film thickness and refractive index that satisfies the formula (3) for the target wavelength of visible light on the surface of the base particles is formed.
- the film having a reflection peak in the visible light castle is formed by alternately repeating coating of a film having a different refractive index once or more on the film.
- the order of the materials to be formed Is determined as follows. First, when the refractive index of the core substrate is high, it is preferable that the first layer be a film having a low refractive index, and in the opposite case, it is preferable that the first layer be a film having a high refractive index.
- the change in optical film thickness which is the product of the film refractive index and the film thickness, is measured and controlled as a reflected waveform using a spectrophotometer or the like.
- the thickness of each layer is adjusted so that the reflected waveform finally becomes the required waveform.
- Design the film thickness For example, if the peak position of the reflection waveform of each unit film constituting a multilayer film is precisely adjusted to a specific wavelength, a single colored powder such as blue, green, and yellow can be obtained without using a dye or pigment. it can.
- phase shift at the interface between the film material and the substrate material, and the peak shift due to the wavelength dependence of the refractive index. is there.
- phase shift occurs, such as elliptically polarized light reflected on the surface of a material with a large metal surface attenuation coefficient. Since it affects the mutual phase of each particle, it is preferable to consider it.
- the interference of a film formed on a curved surface such as a spherical powder occurs in the same way as a flat plate, and basically follows the Fresnel interference principle. Therefore, the coloring method can be designed to a specific color system.
- the light incident on and reflected by the powder causes complex interference.
- These interference waveforms are almost the same as a flat plate when the number of films is small. But, As the number of films increases, the interference inside the multilayer film becomes more complicated.
- the reflection spectral curve can be designed in advance by computer simulation based on the Fresnel interference so that the combination of the film thickness is optimized.
- the effect of the phase shift on the surface of the base particles and all the films is taken into consideration, and a computer simulation is designed so that the combination of the film thicknesses is optimized in advance. Further, the peak shift due to the oxide layer on the surface of the base particles divided by the wavelength dependence of the refractive index is taken into account.
- the designed spectral curve is referred to, and in order to correct these in the actual film, it is optimal to change the film thickness with a spectrophotometer or the like so that the reflection peak is the target wavelength with the final target film number. Must be found.
- phase shift occurs, such as elliptically polarized light reflected on the surface of a material with a large metal surface attenuation coefficient. It is extremely complicated to optimize each of them and obtain the target waveform because they affect the mutual phase of each particle, and to obtain the optimal interference reflection waveform, as described above,
- the optical properties of the material of the film must be determined, and the combination of film thickness and film to obtain the target waveform must be determined in advance by computer simulation based on that value.
- Interference of spherical powder Basic film design is performed with reference to the conditions of the multilayer film.
- the peak position of each unit film constituting the above-mentioned multilayer film can be adjusted by the film thickness of each layer, and the film thickness is determined during the film forming conditions for forming a solid phase component such as a metal oxide on the surface of the base particles.
- the film thickness can be accurately controlled, a film having a uniform thickness can be formed, and a desired color system can be colored.
- the reflection peak wavelength and the number of peaks it is necessary to optimize the sharp reflection peak wavelength and the number of peaks, and the thickness control of each layer is optimized.
- the reflection peak appears within the visible range by changing the viewing angle from outside the visible range, or conversely, if the reflection angle appears in the visible range by changing the viewing angle, it may be a sharp reflection peak. If the viewing angle changes slightly, the color can change at the same time, which is effective.
- the color change due to the color shift can be predicted from the calculated value of the peak position when the incident angle is changed in the combination of the above formula 1 or the formulas 1 and 2.
- the material of the base particles, the particle size of the base particles, the number of coating layers, the coating order of each coating layer, the material of each coating layer, and the desired reflected light wavelength are selected in advance. There is a need to.
- selecting the material of the base particles and each coating layer naturally specifies the refractive index thereof.
- the specification of the refractive index of the base particles and the respective coating layers involves calculation of the Fresnel reflection coefficient and the amplitude reflection intensity between the respective layers.
- the curvatures of the base particles and the multilayer film are specified. If the curvature is not specified, it will be difficult to correct a spectral monitoring characteristic for film thickness monitoring described later.
- the multilayer film reflection intensity R flat is a material (refractive index) of the base particles selected in advance, the number of coating layers, the coating order of each coating layer, the material (refractive index) of each coating layer,
- the desired reflected light wavelength is obtained by applying it to the recurrence formula 1 below and solving it.
- ri j refractive index of the ⁇ th layer from the bottom
- dj thickness of the j-th layer from the bottom
- the multilayer film reflection intensity R flat obtained in the above manner as a method you correct the shape of the base particles is not particularly limited, the R flat value further following formula 2
- each coating layer is determined so that the R ( ⁇ ) value becomes a maximum value or a minimum value at a desired wavelength.
- each coating film is formed on the base particles so as to have the thickness determined as described above.
- monitoring of the film thickness during the film forming operation is performed by measuring the wavelength at which the reflection intensity of the coated object coated with each coating layer becomes the maximum value or the minimum value using a spectrophotometer, and measuring the maximum or minimum value corresponding to the film thickness. It is conceivable to end the film forming operation when the reflection wavelength value is reached.
- the base material is a powder
- the relationship between the maximum or minimum measured value of the reflected wavelength and the film thickness is deviated due to the curvature of each coating layer depending on the particle shape and particle diameter, and the spectrophotometer
- the film is formed so that the maximum or minimum reflection wavelength measured by the method becomes a desired value, there arises a problem that the finally obtained multilayer-coated powder does not have a desired reflection intensity at a desired wavelength.
- the method of this correction is not particularly limited, but each of the coating layers selected on the selected base particles is coated by changing the film thickness stepwise to several types to obtain a film coating powder for particle diameter correction, and the particle diameter correction is performed.
- the actual film thickness value (d M ) of each coating layer of the film coating powder for use was measured, and each of the film coating powders was measured with a spectrophotometer, and the film coating powder for particle size correction was measured.
- each covering to the product (n d M) between the actual thickness value and the refractive index of each coating layer of each particle ⁇ Tadashiyo film-coated powder (n) obtains the ratio of the optical thickness of the layer (nd) (nd / nd M ), a multilayer film reflecting the ratio 2 [delta] "in the intensity obtaining the recurrence formula 1 (nd / nd M) each coating layer is multiplied by the value It is preferable to correct the spectrophotometric characteristics of the powder having the following, and to form each coating layer so as to obtain the corrected spectrophotometric characteristics.
- the method for measuring the actual film thickness (d M ) of each coating layer of the particle-size-correcting film-coated powder is not particularly limited. It is preferable to carry out the measurement by cutting and measuring from the cut surface. Further, the particle ⁇ Tadashiyo when cutting a film-coated powder, be performed by a focused ion beam (FIB) machining, the cut surface becomes clear, the actual thickness value (d M of each coating layer ) Is suitable for measurement. You.
- FIB focused ion beam
- the base particles serving as a control for forming the metal oxide film or the like are not particularly limited, and may be an inorganic substance containing a metal, an organic substance, a magnetic substance, a dielectric substance, or the like. It may be a body, a conductor, an insulator, or the like.
- the substrate is a metal
- any metal such as iron, nickel, chromium, titanium, and aluminum may be used.
- a magnetic material such as iron is preferable.
- These metals may be alloys, and when having the above-mentioned magnetism, it is preferable to use ferromagnetic alloys.
- the base of the powder is a metal compound
- typical examples thereof include oxides of the above-mentioned metals.
- examples thereof include iron, nickel, chromium, titanium, aluminum, and silicon.
- oxides such as calcium, magnesium and barium, or composite oxides thereof may be used.
- examples of metal compounds other than metal oxides include metal nitrides, metal carbides, metal sulfides, metal fluorides, metal carbonates, and metal phosphates.
- the base particles other than metals, they are semimetal and nonmetal compounds, especially oxides, carbides and nitrides, and silica, glass beads and the like can be used.
- Other inorganic materials include inorganic hollow particles such as shirasu balloons (hollow silicate particles), micro carbon hollow spheres (Clekasphere), fused alumina bubbles, aerosil, white carbon, silica micro hollow spheres, and calcium carbonate micro hollow spheres. Mica, calcium carbonate, perlite, talc, bentonite, synthetic mica, muscovite, etc .;
- resin particles are preferable.
- the resin particles include cellulose powder, cellulose acetate powder, polyamide, epoxy resin, polyester, melamine resin, polyurethane, butyl acetate resin, silicone resin, acrylate ester, and methacrylic acid.
- Spherical or crushed particles obtained by polymerization or copolymerization of esters, styrene, ethylene, propylene and derivatives thereof.
- Particularly preferred resin particles are spherical acryl resin particles obtained by polymerization of acrylic acid or methacrylic acid ester.
- the heating temperature in drying must be lower than the melting point of the resin.
- the shape of the substrate may be spherical, subspherical, isotropic such as regular polyhedron, rectangular parallelepiped, spheroid, rhombohedron, plate-like, needle-like (cylinder, prism), etc. Such completely amorphous powders can also be used.
- the size of these substrates is not particularly limited, but is preferably in the range of 0.01 / im to several mm.
- the specific gravity of the substrate particles is in the range of 0.1 to 10.5.
- the fluidity and the floating From the surface it is preferably from 0.1 to 5.5, more preferably from 0.1 to 2.8, and even more preferably from 0.5 to 1.8.
- the specific gravity of the substrate is less than 0.1, the buoyancy in the liquid is too large, and the film needs to be multi-layered or very thick, which is uneconomical.
- it exceeds 10.5 the film for floating becomes thick, which is also uneconomical.
- the interference color is obtained by coating the powder base particles using a plurality of coating layers having different refractive indices and appropriately selecting the refractive index and the layer thickness of each coating layer. As a result, it is possible to obtain a powder colored in a specific color system and exhibiting a specific interference reflection peak besides the visible light castle.
- the coating film of the selected material, number of coatings, and coating order is adjusted so that the reflection intensity R (1) value of the multilayer coating powder becomes the maximum value or the minimum value at the desired wavelength.
- a film is formed so as to have a film thickness determined as desired.
- the coating film to be formed is not particularly limited, except that it has the selected material, the number of coatings, the coating order, and the required film thickness, and examples thereof include those made of a metal compound, an organic substance, and the like.
- the metal used as the metal salt is iron, Eckel, chromium, titanium, zinc, aluminum, cadmium, zirconium, silicon, tin, lead, lithium, indium, neodymium, bismuth, cerium, antimony. And calcium, magnesium, barium and the like.
- salts of these metals examples include sulfuric acid, nitric acid, hydrochloric acid, oxalic acid, and salts of carbonic acid and carboxylic acid.
- a chelate complex of the metal is also included.
- the kind of the metal salt used in the present invention is selected according to the properties to be imparted to the surface of the substrate and the means to be applied in the production.
- the powder of the present invention basically forms a colorless and transparent film, and is colored by laminating films having different refractive indices. Therefore, the above-mentioned metals and salts thereof are mentioned. If the waveform of the reflection and absorption spectrum does not have the desired color, the following metal cobalt, yttrium, sulfur, europium, dysprosium, antimony, samarium, copper, silver, gold, platinum, rhodium, Sulfuric acid, nitric acid, hydrochloric acid, oxalic acid, carbonic acid, and salts of carboxylic acids of metals such as iridium, tandatin, iron, and manganese. Further, a chelate complex of the metal is also included. The content of these metals in the film is 10 ppm to 15%, preferably 10 ppm to 15%, and more preferably 50 ppm to 5%.
- a film of a metal oxide or the like using these metal salts may be formed in a plurality of layers, and a metal oxide or the like obtained by hydrolysis of a metal alkoxide, if necessary, on the film of the metal oxide or the like.
- a film can be formed by another film forming method.
- a multilayer film can be formed on the substrate particles, and at this time, by setting the forming conditions so that the thickness of each layer has a predetermined thickness, the desired characteristics can be obtained. It is possible to form a multi-layered film of a metal oxide or the like by using a metal salt, which is an inexpensive substance, with a simple operation. In particular, it is an important advantage that a powder coated with a multilayer film can be obtained without using an expensive metal alkoxide as a raw material.
- a multi-layer coating film may be manufactured as a continuous process, and each coating film may be manufactured one by one, or a single layer may be manufactured. It can be manufactured by various methods, for example, by combining the multi-layer continuous manufacturing.
- the particle size of the film-coated powder according to the present invention is not particularly limited, and a force that can be appropriately adjusted according to the purpose is usually 0.1 ⁇ to several mm, more preferably 0.1 ⁇ m. 330 ⁇ m.
- the preferable thickness range of one layer of the film-coated powder of the present invention varies depending on the film material and the size of the particles serving as the substrate.
- the film material is a metal or a material having a large absorption coefficient such as an opaque metal oxide or metal sulfide
- the substrate particle is 0.1 ⁇ m to 111 ⁇ m and the body particle force is 1 ⁇ m to 0.5 ⁇ m.
- the diameter f be 0.01 m to 0.7 ⁇ m at 10 ⁇ m, and 0.001 ⁇ to 1.0 m when the base particles are 10 111 or more.
- the substrate particles should be 0.1 ⁇ m to 1 ⁇ m and 0.1 ⁇ m to 1.5 ⁇ m. It is preferable that the average particle diameter is 1 ⁇ m to 10 m and 0.1 ⁇ m to 3.0 ⁇ m, and the average particle diameter is 0.1 ⁇ m to 5.0 ⁇ m when the base particles are 10 ⁇ m or more.
- the preferable thickness range of the total film thickness of the film-coated powder of the present invention also varies depending on the size of the particles serving as the substrate.
- Substrate particles are 0.1 ⁇ ⁇ ! 0.1 ⁇ ⁇ 5 ⁇ m for ⁇ 1 ⁇ m, 1 ⁇ ! 0.1 ⁇ for ⁇ 10 ⁇ m!
- the thickness is preferably 0.1 im to 20 ⁇ m.
- the film-coated powder and the coating composition of the present invention can be used in a film-forming reaction in the production method, particularly when a film-forming reaction is carried out in an aqueous solvent, under a pH-determined condition as a film-forming reaction solvent.
- the film is formed by a film-forming reaction on the surface of the substrate at the same time using a water-based solvent and a film coating reaction under ultrasonic dispersion conditions.
- a buffer solution is added to an aqueous solvent to make a buffer solution, or a buffer solution prepared in advance is used in order to keep the membrane formation reaction constant.
- a film material other than the buffer solution is added to form a film. If the pH fluctuates greatly when the film is formed by adding the film forming raw materials, it is desirable to add a buffer solution to prevent this from occurring.
- the pH-determination means that the pH is within ⁇ 2 of a predetermined pH, preferably within 1 soil, more preferably within ⁇ 0.5.
- the buffer solution Various systems are used for the buffer solution, and are not particularly limited. It is important to be able to disperse, and at the same time, the metal hydroxide or metal oxide film-coated powder deposited on the surface of the substrate can be dispersed by the action of the electric double layer, and a dense film is formed by the above-mentioned gentle dripping reaction. Satisfies the conditions for film formation
- the method for producing a film-coated powder of the present invention can be different from the conventional method of neutralization by reaction of a metal salt solution, precipitation at an isoelectric point, or decomposition by heating to precipitate.
- the ultrasonic dispersion conditions various ultrasonic oscillators can be used, for example, a water tank of an ultrasonic cleaner can be used, and there is no particular limitation.
- the ultrasonic dispersion conditions of the present invention vary depending on the size of the oscillator, the shape and size of the reaction vessel, the amount and volume of the reaction solution, the amount of the base particles, and the like. You only have to select appropriate conditions.
- the buffer solution used in the present invention depends on the solid phase component to be precipitated and is not particularly limited, but is based on Tris, boric acid, glycine, succinic acid, lactic acid, acetic acid, and tartaric acid. And hydrochloric acid type.
- a method of forming an alternate multilayer film of a metal oxide having a high refractive index and a metal oxide having a low refractive index, particularly when a film forming reaction is performed in an aqueous solvent will be specifically described.
- a coating such as titanium oxide or zirconium oxide
- the base particles are immersed in a buffer solution such as an acetic acid / sodium acetate system and dispersed by ultrasonic oscillation to obtain a metal salt such as titanium or zirconium. Titanium, zirconium sulfate, etc.
- this powder is separated into solid and liquid, washed and dried, and then heat-treated.
- the drying means may be either vacuum drying or natural drying. It is also possible to use a device such as a spray dryer in an inert atmosphere.
- the formation of titanium oxide is It is shown by the above reaction formula.
- T i 0 2 content of titanyl sulfate may lay preferred is 5 g / liters ⁇ 1 80 gZ liters, more preferably 1 0 gZ l ⁇ 1 60 g / l. If the amount is less than 5 g / liter, it takes too much time to form a film, and the amount of powder to be processed is reduced, which is uneconomical.If the amount exceeds 180 g / l, the diluting solution is hydrolyzed during the addition, and the film is formed. They are both unsuitable.
- this powder is separated into solid and liquid, washed and dried, and then heat-treated.
- this operation by repeating the operation of forming two layers of metal oxide films having different refractive indexes on the surface of the base particles, a powder having a multilayer metal oxide film on the surface can be obtained.
- silicon dioxide When the film to be coated is silicon dioxide, the formation of silicon dioxide is represented by the following reaction formula.
- JP-A-6-228604, JP-A-7-90310 or International Publication WO 96/28269 previously proposed by the present inventors The aqueous method described in JP-A-11-113102 is preferred.
- the linear growth rate is set higher than the solid phase deposition rate, and the reaction conditions are adjusted so that an amorphous uniform film is formed.
- the organic substance is not particularly limited, but is preferably a resin.
- the resin include cellulose, cellulose acetate, polyamide, epoxy resin, polyester, melamine resin, polyurethane, bieryl acetate resin, silicone resin, etalinoleate ester, metaatalinolate ester, styrene, ethylene and propylene. And polymers or copolymers of these derivatives.
- CVD Vapor-phase film forming method
- the base particles are made of a substance having a high refractive index, a light-transmitting film having a low refractive index is provided thereon, and a particle constituting film having a high refractive index is further provided thereon, and further, And a light-transmitting film having a low refractive index are sequentially and alternately provided.
- a high-refractive-index particle-constituting film is formed thereon, a low-refractive-index light-transmitting film is further formed thereon, and a high-refractive-index particle-forming film is further formed thereon
- a high-refractive-index particle-forming film is further formed thereon
- Raw materials used to form high refractive index films include titanium halides and sulfates for titanium oxide films, and zirconium halides and sulfates for zirconium oxide films. Carboxylates, oxalates, chelate complexes, etc. For cerium oxide films, cellium halides, sulfates, carboxylate, oxalate, etc. For bismuth oxide films, bismuth halides, nitrates For indium oxide films, such as carboxylate and carboxylate, indium halide, sulfate and the like are preferable.
- a silicon oxide film As a raw material used to form a film having a low refractive index, for a silicon oxide film, an organic silicon compound such as sodium silicate, water glass, silicon halide, alkyl silicate and the like are used.
- an organic silicon compound such as sodium silicate, water glass, silicon halide, alkyl silicate and the like are used.
- aluminum oxide films such as polymers, aluminum Magnesium sulfates, halides and the like are preferable for magnesium oxide films such as halides, sulfates and chelate complexes.
- mixing titanium chloride with titanium chloride has an effect of forming a rutile type titanium oxide film having a higher refractive index at a lower temperature.
- a more complete oxide film can be manufactured by controlling the reaction temperature at the time of coating to a temperature suitable for each type of metal salt.
- the reaction system can be heated to accelerate the solid phase deposition reaction.
- the heat treatment of heating is excessive, the reaction rate is too fast, and the supersaturated solid phase does not form a film, but precipitates in an aqueous solution to form a gel or fine particles, making it difficult to control the film thickness. Become.
- the inclined washing is repeated while adding distilled water to remove the electrolyte, followed by heat treatment such as drying and baking to remove the water contained in the solid phase and completely remove the acid. It is preferable to use an oxide film.
- heat treatment such as drying and baking to remove the water contained in the solid phase and completely remove the acid.
- heat treatment may be performed each time each layer is coated, or heat treatment may be performed at the end after completion of the desired multilayer film.
- the heat treatment conditions vary depending on the reaction system, but the heat treatment temperature is from 200 to 130 ° C., preferably from 400 to 110 ° C. If the temperature is lower than 200 ° C., salts and moisture may remain. If the temperature is higher than 130 ° C., the film and the substrate may react with each other to form another substance, and both are unsuitable.
- the heat treatment time is from 0.1 to 100 hours, preferably from 0.5 to 50 hours.
- a medium (vehicle) of a specific color ink or a paint-like composition (fluid) a conventionally known varnish used for color printing, color magnetic printing, and color magnetic paint is used.
- a conventionally known varnish used for color printing, color magnetic printing, and color magnetic paint is used.
- a polymer or monomer dissolved in a solvent can be appropriately selected and used depending on the type of powder, the method of applying the ink, and the application.
- liquid polymer examples include diene such as polypentadiene and polybutadiene, polyethylene glycols, polyamides, polypropylenes, waxes, and knitted copolymers thereof.
- Polymers soluble in organic solvents include olefin polymers, acrylic resins such as oligoester acrylate, polyesters, polyamides, polyisocyanates, amino resins, xylene resins, ketone resins, and gen resins. Examples thereof include resins, rosin-modified phenolic resins, gen-based rubbers, chloroprene resins, hexes, and modified or copolymers thereof.
- Examples of the monomer soluble in the organic solvent include styrene, ethylene, butadiene, and pyrene.
- organic solvent examples include alcohols such as ethanol, isopropanol and normal propanol, ketones such as acetone, benzene, toluene, xylene, kerosene, benzene hydrocarbons, esters, ethers, and modified products and copolymers thereof. And the like.
- the specific color-based toner, the specific color-based dry ink, and the specific color-based dry paint-like composition (powder) are obtained by combining the above-mentioned specific color-based multi-layer coating powder with a resin or, if necessary, a toning material. Is kneaded directly with a screw-type extruder, roll mill, ada, etc., coarsely pulverized with a hammer mill or cutter mill, finely pulverized with a jet mill, etc., and classified into the required particle size with an elbow jet, etc. to obtain a powdery cyan color. Material composition can be obtained. Further, the powder coated with the specific color system multilayer film can be made into a powdery specific color system coating composition by using a polymerization method such as an emulsion polymerization method or a suspension polymerization method.
- a polymerization method such as an emulsion polymerization method or a suspension polymerization method.
- the powder coated with the specific color multi-layer film, the resin, and additives such as a toning agent and a solvent can be liquefied with a three-roll colloid mill to obtain a liquid specific color coating composition such as an ink paint.
- a white pigment for example, titanium oxide, zinc oxide, tin oxide, silicon oxide, antimony oxide, lead oxide or the like is used.
- These composite oxides, carbonates such as calcium carbonate, magnesium carbonate, barium carbonate, etc .; sulfates such as barium sulfate and calcium sulfate; sulfides such as zinc sulfate; or the above oxides, carbonates and sulfuric acid A composite oxide obtained by sintering a salt and a composite hydrated oxide may be used.
- Blue pigments are used to adjust saturation and hue, especially when used for color reproduction in full-color mixing.
- organic pigments oxide sulfide composite pigments such as ultramarine , Iron blue, milori blue, etc., copper-based ultramarine blue pigments, cobalt oxide, cobalt oxide-based composite oxides, such as cerulean blue, blue pigments, blue organic dyes and pigments, and blue inorganic pigments Alli-Li Blue Lake, Peacock Lake dyes such as blue lake, lake pigments, non-metallic lid cyanine, Phthalocyanine-based dyes and pigments such as phthalocyanine, and chromium-based oxides such as chrome green, zinc green, chromium oxide, and hydrated chromium (Viridian), which are green pigments.
- organic pigments oxide sulfide composite pigments such as ultramarine , Iron blue, milori blue, etc., copper-based ultramarine blue pigments, cobalt oxide, cobalt oxide-based composite oxides, such as cerulean blue, blue pigments, blue organic dyes and pigments, and blue inorgan
- Pigments inorganic pigments such as cobalt oxides such as cobaltdiv, nitroso pigments such as pigment green and naphthole green, azo pigments such as green gold, phthalocyanine pigments such as phthalocyanine green and polychrome copper phthalocyanine; Lake dyes such as malachite green lake and acid green lake, oil dyes, oil dyes and pigments, and organic dyes and pigments such as alcohol dyes such as alcohol blue.
- the present invention is not limited only to these.
- pigments or dyes such as blue, yellow, and magenta for delicate color tone control
- the resin produced by the above-mentioned pulverization method is not particularly limited, but may be polyamide, epoxy resin, polyester, melamine resin, or the like. Polyurethane, butyl acetate resin, silicone resin, Atari Estenole luate, Estenole meta-atalinoleate, styrene, ethylene, butadiene, propylene, and polymers or copolymers of these derivatives.
- the polymerization is started from one or a mixture of esters, urethanes, butyl acetate, organic silicon, atarilic acid, methacrylic acid, styrene, ethylene, butadiene, propylene, etc. A coalescence or a copolymer thereof is formed.
- the coating composition containing the film-coated powder of the present invention comprises (1) each specific color ink or paint-like composition (fluid) and (2) each specific color toner, and each specific color dry type. It takes the form of an ink-like composition (powder).
- a fluid it is a specific color ink or paint, etc .; the toning material; a solidifying accelerator for late drying resin; a thickener for increasing the viscosity; and a fluid for decreasing the viscosity.
- a component such as a dispersant or a dispersant may be included for dispersing the agent and the particles.
- a solidification accelerator is used for the toning material, a resin that is slowly dried, and a fluid is used to reduce the viscosity during kneading.
- components such as a dispersing agent, a charge controlling agent for fixing to paper or the like, and a wax can be included.
- the toning material When the polymerization method is used, the toning material, polymerization initiator, polymerization accelerator, thickener to increase the viscosity, dispersant to disperse the particles, fixing to paper, etc.
- components such as a charge control agent and wax can be included.
- the multi-layer coating powder in each color-based coating composition of the present invention can be formed by a single powder or a combination of a plurality of powders having different spectral characteristics by wet or dry color printing or wet and dry color magnetic printing.
- the three primary color powders are used to identify six combinations of visible light, non-visible light (ultraviolet and cyan), fluorescent color and magnetism, and electricity (electric field change). It has a function and can be applied to other applications that require a security function, such as color magnetic ink for preventing forgery of printed matter.
- the above-mentioned coating composition of the present invention is used as a base material as each specific color system ink or paint-like composition or each specific color system toner, each specific color system dry ink-like composition, and each specific color system dry coating composition.
- the relationship between the content of the resin coated with the fixed color multi-layer film and the content of the resin is 1: 0.5 to 1:15 in volume ratio. If the content of the medium is too small, the applied film does not adhere to the object to be coated. On the other hand, if the amount is too large, the color of the pigment becomes too light and cannot be called a good ink or paint.
- the relationship between the amount of the solvent and the total amount of each color system or each color material in the coating composition and the amount of the solvent is 1: 0.5 to 1:10 by volume ratio. If the amount is too small, the viscosity of the paint is so high that it cannot be applied uniformly. On the other hand, if the amount of the solvent is too large, it takes time to dry the coating film, and the efficiency of the coating operation is extremely reduced.
- the color density of the coating film when printed, melt-transferred or coated on the substrate is determined by the amount of pigment per unit area of the substrate.
- the amount of the multi-layer coating powder of each color system of the present invention on the object to be coated is 0.1 to 300 g per square meter in terms of area density when uniformly applied, and is preferable. If 0.1 is 100 g, a good coating color can be obtained. If the area density is smaller than the above value, the ground color of the object to be coated appears, and if the area density is larger than the above value, the color density of the coating color does not change, which is uneconomic.
- the thickness of the coating film is reduced. This is not the case even when a specific design or the like is partially formed. Examples>
- the design was such that the vertical reflection color was red and the reflection color for 50 degree incident light was blue. (Formation of the first layer titania film)
- silica-coated granular aluminum powder A1 To 2 Og of silica-coated granular aluminum powder A1, add 375 1 g of buffer solution 1 and 3 13 ml of pure water prepared in advance, and in a 28 kHz, 600 W ultrasonic bath. While applying ultrasonic waves, the particles were dispersed in a buffer solution 1 containing aluminum powder with stirring. To this, a 1400 ml aqueous sodium silicate solution also prepared in advance was gradually added in 2.67 ml, and a silicon film was deposited on the surface.
- the slurry containing the film-forming powder was repeatedly decanted and washed with sufficient water.
- silica film powder After washing, the silica film powder is put into a vat, sedimented and separated, the upper solution was discarded, and then dried in air at 150 ° C for 8 hours using a dryer, and silica Z tita coat granular aluminum powder was used. I got A2.
- aqueous solution 4 Dissolve 0.9 mol of sodium acetate in 1 liter of water to obtain aqueous solution 4.
- Aqueous solution 3, aqueous solution 4, and pure water are mixed at a volume ratio of 50: 100: 250 to obtain buffer solution 2.
- This powder was reddish yellow and had a maximum reflection peak at 667 nm.
- the slurry containing the film-forming powder was repeatedly decanted and washed with sufficient water.
- the unreacted portion was gradually precipitated as solid fine particles, and the fine particles were taken into the film.
- decantation is repeated with sufficient pure water to remove the unreacted portion and excess sulfuric acid and the sulfuric acid formed by the reaction, to perform solid-liquid separation. I got
- the obtained dried powder was subjected to a heat treatment (baking) at 65 ° C. for 30 minutes in a rotary tube furnace to obtain a silica / titer-coal granular aluminum aluminum powder A.
- This five-layer film-coated powder A was bright red and had a maximum reflection peak of 718 nm.
- the peak wavelength of the spectral reflection curve of each of the above film-coated powders, the reflectance at the peak wavelength, the refractive index of the coating film, the film thickness, the peak height (H), the half width (W) and the ratio (H / W) was measured by the following method.
- Table 1 shows the thicknesses of the first to fifth layers, the peak wavelength of the spectral reflection curve of the film-coated powder, the peak height (H), the half width (W), and the ratio (H / W).
- Acrylic resin varnish (Ata Riddick A405) 35 parts by weight
- Epoxy resin varnish (Ebon 100 1: 50% liquid) 10 parts by weight
- the obtained coating composition A was uniformly applied to an iron plate in a draft equipped with an exhaust device. After the application, the plate was dried at room temperature, and further dried by heating at 160 ° C. for 3 hours in a box drier to obtain a coated plate A.
- the color of the obtained coating plate A when viewed vertically was red.
- the color at which the coated plate was inclined by 50 degrees was blue.
- the vertical reflection color was designed to be yellow.
- the slurry containing the silica film-forming powder was repeatedly decanted and washed with sufficient water.
- silica-coated granular aluminum powder B1 was obtained.
- the decantation is repeated with sufficient pure water to remove the unreacted portion and excess sulfuric acid and the sulfuric acid formed by the reaction.
- the solid-liquid separation is performed, and the dried powder is dried after drying in a vacuum dryer. Obtained.
- the obtained dried powder was subjected to heat treatment (firing) at 650 ° C. for 30 minutes in a rotary tube furnace to obtain silica Z tita-acoto granular aluminum powder B2.
- This powder was reddish yellow and had a maximum reflection peak at 667 nm.
- the slurry containing the silica film-forming powder was repeatedly decanted and washed with sufficient water.
- silica film powder After washing, the silica film powder is put into a vat, sedimented and separated, the upper solution was discarded, and dried in a dryer at 150 ° C for 8 hours in air, and silica Z titania-coated granular aluminum powder B Got three.
- the decantation is repeated with sufficient pure water to remove unreacted components, excess sulfuric acid and sulfuric acid formed by the reaction, and then perform solid-liquid separation. Obtained.
- the obtained dried powder was subjected to a heat treatment (calcination) at 650 ° C. for 30 minutes in a rotary tube furnace to obtain silica Z titania-coated granular aluminum powder B4.
- This four-layer film-coated powder B was bright green and had a maximum reflection peak at 558 nm. (Fifth layer of ferric oxide)
- silica membrane and the aqueous buffer solution for titanium buffer, 3,20 Om1 which were put in a container in a water bath, were kept at 90 ° C, and B4 and 20 g were added thereto and sufficiently stirred and dispersed. .
- ferrous sulfate (tetrahydrate) 0.1M—45m1 and ferric sulfate (nhydrate: n is about 10.38) 0.2M—45m1 acidic mixture The solution was added dropwise at 0.7 ml / min. After the dropwise addition, the mixture was reacted for 2 hours while stirring was continued.
- the electrolyte was removed by slant washing using sufficient pure water. After the solid-liquid separation, the powder is dried at 110 ° C for 8 hours.After the drying is completed, the powder is heat-treated at 650 ° C in a rotary tube furnace in a nitrogen atmosphere, and the granular aluminum powder is coated with silica Z titania Z. B was obtained.
- the color of the obtained powder B was 70% with a reflection peak of 606 nm, and the color was bright yellow.
- Table 2 shows the film thickness of the first to fifth layers, the peak wavelength of the spectral reflection curve of the film-coated powder, the peak height (H), the half width (W), and the ratio (H / W).
- Acrylic resin paper (Ataridick, A405) 64 Melamine resin varnish (S, -perbecamine, J820) 28 parts by weight Powder B 5 parts by weight
- Powder B was added to a mixed solution of xylene and silicone, and the mixture was dispersed with a high-speed stirrer for 5 minutes. Resin varnish was added and melamine resin varnish was added to make it sufficiently uniform. A coating composition B was obtained.
- the obtained coating composition B was uniformly applied to an iron plate in a draft equipped with an exhaust device. After the application, the plate was dried at room temperature, and further dried by heating at 160 ° C. for 3 hours using a box drier to obtain a coated plate B.
- the color of the obtained coating plate B when viewed vertically was yellow.
- the color of the coated plate inclined at 50 degrees was reddish purple.
- Example 3 (Catalyst coating composition using muscovite)
- spherical muscovite mica powder As the base particles, 20 g of spherical muscovite mica powder (average particle diameter: 13.3 ⁇ ) was sufficiently dispersed in a buffer solution '2 of 2,626 m 1 in an ultrasonic bath. Thereafter, while maintaining the temperature of the solution at 50 to 55 ° C., 58 m 1 of an aqueous titanium sulfate solution prepared in advance was gradually dropped at a constant rate of 1.8 m 1 / min. After dropping, the mixture was reacted for 2 hours to obtain titania-coated muscovite powder C1.
- a silica film was formed on 15 g of the titania-coated muscovite powder C1. Film formation was carried out with a buffer solution volume of 3,751 m1 and a dropping rate of sodium silicate aqueous solution of 40 m1 / min.The reaction was allowed to proceed for 2 hours until no unreacted substances were left. After washing, heat treatment (firing) is performed in a rotary tube furnace at 500 ° C for 30 minutes in a nitrogen atmosphere, and silica / titer-coated muscovite powder having a dense titer film is obtained. C2 was obtained.
- This three-layer film-coated powder C3 was reddish and had a maximum reflection peak at 787 nm.
- Table 3 shows the thicknesses of the first to third layers, the peak wavelength of the spectral reflection curve of the film-coated powder, the peak height (H), the half width (W), and the ratio (HZW).
- a paint was prototyped with the following compounding ratio.
- Soybean stand oil 8.1 parts by weight
- the obtained coating composition C was uniformly applied to an iron plate in a draft provided with an exhaust device. After the application, the plate was dried at room temperature, and further dried by heating at 160 ° C. for 3 hours using a box drier to obtain a coated plate C.
- the color of the obtained coating plate C when viewed vertically was red.
- the color at which the coated plate was inclined by 50 degrees was blue.
- Example 4 Coating composition using oxide film-coated plate-like iron powder having a large color shift
- the vertical reflection color was gray and the reflection color for 30 degree incident light was green.
- the slurry containing the silica film-forming powder was repeatedly decanted and washed with sufficient water.
- Aqueous solution 3, aqueous solution 4, and pure water are mixed at a volume ratio of 50: 100: 250 to obtain buffer solution 2.
- Titanium sulfate as T i 0 2 concentration of 1 0 w 1% was added to water, adjusting the concentration to obtain a titanium sulfate aqueous solution.
- the slurry containing the silica / titania film-forming powder was washed by repeating decantation with sufficient water.
- the maximum reflection peak of this 5-layer film-coated powder D was 392 nm and 557 nm, and was gray.
- Table 4 shows the film thickness of each of the first to fifth layers, the peak wavelength of the spectral reflection curve of the film-coated powder, the peak height (H), the half width (W), and the ratio (H / W). (Table 4)
- the powder D was dispersed in 100 ml of a xylene solution containing 5% of ataryl resin, and the dispersion was applied to art paper with a blade coater.
- magenta color around 390 nm and the green color at 557 nm are just complementary colors, and both are added to make it achromatic, but with a slight tilt, the magenta color around 390 nm disappears from the visible range. It is probable that green appeared in the visible region, and the green disappeared when tilted, and the green peak disappeared when tilted sufficiently, and the next reddish purple peak appeared from the infrared region.
- the design is such that the vertical reflection color is green and the 50 degree incident light is red.
- silica-coated plate-like iron powder E1 was dispersed in 198.3 g of ethanol and 17.9 g of titanium isopropoxide were added in advance, followed by stirring. Meanwhile, a solution prepared by mixing 30.4 g of pure water with 47.9 g of ethanol prepared in advance was added dropwise over 1 hour. After the addition, the reaction was carried out at room temperature for 5 hours. After the reaction, the mixture was diluted and washed with sufficient ethanol, filtered, and dried in a vacuum drier at 110 ° C. for 3 hours, to obtain silica Z titaniacot sheet iron powder E2. This E 2 had a peak wavelength of a spectral reflection curve at 540 nm and was dark green. (Adjustment of buffer solution 1)
- silica / titania-coated sheet iron powder E2 To 22 g of silica / titania-coated sheet iron powder E2, add 3751 g of buffer solution 1 and 313 ml of pure water prepared in advance, and add 28 kHz, 600 W While applying ultrasonic waves in an ultrasonic bath, the particles were further dispersed in a buffer solution 1 containing iron powder with stirring. To this, an aqueous solution of sodium silicate of 140 Om 1 also prepared in advance was gradually added at 2.67 ml / min to deposit a silica film on the surface.
- the slurry containing the film-forming powder was washed repeatedly with decantation with sufficient water. After washing, put the silica film powder into a pad, separate by sedimentation, discard the upper solution, and dry in a dryer at 150 ° C for 8 hours in air, silica Z titania-coated sheet iron powder E Got 3
- the aqueous solution 3, the aqueous solution 4, and pure water are mixed at a volume ratio of 50: 100: 250 to obtain a buffer solution 2.
- decantation is repeated with sufficient pure water to remove the unreacted components and the sulfuric acid formed by the excess sulfuric acid reaction, and perform solid-liquid separation, followed by drying with a vacuum dryer. Later, a dry powder was obtained.
- the obtained dried powder was subjected to heat treatment (firing) at 650 ° C. for 30 minutes in a rotary tube furnace to obtain silica // titania-coated sheet iron powder E.
- the powder was green and had a maximum reflection peak at 543 nm.
- Table 5 shows the thicknesses of the first to fourth layers, the peak wavelength of the spectral reflection curve of the film-coated powder, the peak height (H), the half width (W), and the ratio (H / W).
- 2nd layer titanium : a film 55 540 35 44 0.795
- Coating solution E was produced with the following compounding ratio.
- Resin solution P AM SP-67 (Mitsui Toatsu Chemicals)
- Powder E was put into the resin solution, and pure water was added thereto with stirring to obtain a coating liquid EL.
- the coating liquid EL was uniformly applied on art paper, and the applied amount of the powder was 51 g Zm 2 .
- the vertical color of the coated paper was green, and the maximum reflection peak was 560 nm.
- the vertical reflection color was designed to be reddish purple.
- the slurry containing the silicon film-forming powder was repeatedly decanted and washed with sufficient alcohol.
- silica film powder After washing, put the silica film powder into a pad, sediment and separate, discard the upper solution, and dry in a vacuum dryer at 150 ° C for 8 hours in air. Heat treatment was performed at 30 ° C. for 30 minutes, and after cooling, silica-coated iron powder F1 was obtained.
- TEOS tetraorthosilicate
- the slurry containing the titania / silica film forming powder was repeatedly decanted with sufficient alcohol and washed.
- This F5 had peak wavelengths of the spectral reflection curves at 382 nm and 821 nm, and also had valleys at 356 nm, 556 nm and 900 nm, and was a purplish red powder.
- the magnetization of F5 at 10k0e was 170 emu / g.
- Table 6 shows the film thickness of the first to fifth layers, the peak wavelength of the spectral reflection curve of the film-coated powder, the peak height (H), the half width (W), and the ratio (H / W).
- the vertical reflection color was designed to be reddish purple.
- a separable flask 20 g of granular Carboel iron powder (average particle size: 1.8 ⁇ m) was added to an ethanol mixed solution obtained by mixing 196 g of ethanol, 10 g of pure water, and 1 Og of ammonia. After dispersing with an ultrasonic disperser for 5 minutes, 6 g of tetraorthosilicate (TE0S) was added while stirring with a stirrer, and reacted for 5 hours.
- TE0S tetraorthosilicate
- the slurry containing the silica film forming powder was repeatedly decanted and washed with sufficient alcohol.
- silica membrane powder After washing, put the silica membrane powder into a vat, settle and separate, discard the upper solution, dry in a vacuum dryer at 150 ° C for 8 hours in air, and then dry in a rotary tube furnace. 30 at ° C After a partial heat treatment and cooling, a silica-coated iron powder G1 was obtained.
- This G2 had a peak wavelength of a spectral reflection curve at 451 nm and was cyan. (Formation of third layer silica film)
- titania / silica-coated iron powder G2 To 20 g of titania / silica-coated iron powder G2, prepare an ethanol mixed solution obtained by mixing ethanol 196 g, pure water 1 Og, and ammonia 1 Og, and add iron powder G2 to the solution. After dispersing with an ultrasonic disperser for 5 minutes, 6 g of tetraorthosilicate (TE0S) was added while stirring with a stirrer, and reacted for 5 hours.
- TE0S tetraorthosilicate
- the slurry containing the silica film forming powder was repeatedly decanted and washed with sufficient alcohol.
- This titanium oxide film had peak wavelengths of spectral reflection curves at 380 nm and 820 nm, and further had valleys at 355 nm, 556 nm, and 902 nm, and was purple-red.
- the magnetic resonance ratio of the powder G5 at 10k0e was 140 emu / g.
- Table 7 shows the thicknesses of the first to fifth layers, the peak wavelength of the spectral reflection curve of the film-coated powder, the peak height (H), the half width (W), and the ratio (HZW).
- Pattern 1 was printed using PG10 manufactured by Riso Kagaku to obtain a printed matter PF for discrimination.
- the pattern “A” was printed with the ink-like composition LG using PG10 manufactured by Riso Kagaku, and the surrounding area was printed using LF to obtain a printed matter PF for discrimination.
- the printed matter PF was viewed vertically, the entire surface was reddish purple, but when the viewing angle was changed and it was tilted by about 30 degrees, the letter ⁇ AJ changed to green and the surroundings remained reddish purple. .
- the authenticity can be easily determined by visual inspection.
- the vertical reflection color was designed to be yellow-green.
- a separable flask add 30 g of plate-like iron powder (average particle size: 15 ⁇ m) to an ethanol mixed solution obtained by mixing ethanol (196 g), pure water (10 g), and ammonia (1 Og), and ultrasonic waves After dispersing with a disperser for 5 minutes, 6 g of tetraorthosilicate (TE0S) was added while stirring with a stirrer, and reacted for 5 hours.
- ethanol mixed solution obtained by mixing ethanol (196 g), pure water (10 g), and ammonia (1 Og)
- 6 g of tetraorthosilicate (TE0S) was added while stirring with a stirrer, and reacted for 5 hours.
- the slurry containing the silica film forming powder was repeatedly decanted and washed with sufficient alcohol.
- silica film powder After washing, put the silica film powder into a pad, sediment and separate, discard the upper solution, and dry in a vacuum dryer at 150 ° C for 8 hours in air. Heat treatment was performed at 30 ° C for 30 minutes, and after cooling, silica-coated iron powder HI was obtained.
- This H 2 had a peak wavelength of a spectral reflection curve at 455 nm and was cyan. (Formation of third layer silica film)
- ethanol mixed solution was prepared by mixing ethanol 196 g, pure water 10 g, and ammonia 10 g, and powder H2 was added to the mixed solution. After dispersing with an ultrasonic disperser for 5 minutes, 6 g of tetraorthosilicate (TEOS) was added while stirring with a stirrer, and reacted for 5 hours.
- TEOS tetraorthosilicate
- the slurry containing the titania / silica film-forming powder was repeatedly decanted with sufficient alcohol and washed.
- the titania / silica film powder is put into a pad, sedimentation-separated, and the upper solution is discarded.
- the resulting solution is dried in a vacuum dryer at 150 ° C for 8 hours in air. Heat treatment was performed at 0 ° C. for 30 minutes, and after cooling, silica-coated iron powder H 3 was obtained.
- a liquid was prepared by adding 22 g of titaniumisopropoxide to 198.3 g of ethanol in advance, and the powder H3 was placed in a separable flask. After dispersion in the liquid, a solution prepared by mixing 30.4 g of pure water prepared in advance with 47.9 g of ethanol was added dropwise with stirring over 1 hour. After the addition, the reaction was carried out at room temperature for 4 hours. After the reaction, dilute and wash with sufficient ethanol, separate into solid and liquid, dry with a vacuum dryer at 110 ° C for 3 hours, and after drying, heat treat at 65 ° C for 30 minutes in a rotary tube furnace. After cooling, titania / silica-coated iron powder H 4 was obtained.
- This H4 had a peak wavelength of a spectral reflection curve at 450 nm and was cyan. (Formation of 5th layer titania film)
- a solution prepared by adding 22 g of titanium isopropoxide to 198.3 g of ethanol in advance with respect to 20 g of the titania / silica-coated iron powder H 4 was prepared. Then, a solution prepared by mixing 30.4 g of pure water prepared in advance with 47.9 g of ethanol was added dropwise with stirring over 1 hour. After the addition, the reaction was carried out at room temperature for 4 hours. After the reaction, dilute and wash with sufficient ethanol, separate into solid and liquid, dry with a vacuum drier at 110 ° C for 3 hours, and heat-treat at 65 ° C for 30 minutes in a rotary tube furnace after drying. After cooling, powder H5 was obtained.
- Powder H5 was dispersed in the silver solution, and 200 ml of the above reducing solution was added thereto with stirring. After the addition, the mixture was allowed to react for 30 minutes. After the completion of the reaction, the solid was separated by washing with decantation, followed by solid-liquid separation. It was dried in a dryer at 250 ° C. for 8 hours.
- Table 8 shows the thicknesses of the first to sixth layers, the peak wavelength of the spectral reflection curve of the film-coated powder, the peak height (H), the half width (W), and the ratio (HZW).
- the vertical reflection color was designed to be yellow-green.
- the slurry containing the silica film forming powder was repeatedly decanted and washed with sufficient alcohol.
- silica membrane powder After washing, put the silica membrane powder into a vat, settle and separate, discard the upper solution, dry in a vacuum dryer at 150 ° C for 8 hours in air, and then dry in a rotary tube furnace. Heat treatment was performed at 30 ° C. for 30 minutes, and after cooling, silica-coated iron powder I1 was obtained.
- silica-coated iron powder I1 For 20 g of the silica-coated iron powder I1, 17.9 g of titanium isopropoxide was prepared in advance in 198.3 g of ethanol, and the powder HI was added to the liquid in a separable flask and dispersed therein. While stirring, a solution prepared by mixing 30.4 g of pure water with 47.9 g of ethanol was added dropwise over 1 hour. After the addition, the reaction was carried out at room temperature for 4 hours. After the reaction, the mixture is diluted and washed with sufficient ethanol, separated into solid and liquid, dried in a vacuum dryer at 110 ° C for 3 hours, dried, and heat-treated in a rotary tube furnace at 65 ° C for 30 minutes. After cooling, titania / silica-coated iron powder I2 was obtained.
- This titanium oxide film has a peak wavelength of a spectral reflection curve at 451 nm and is cyan.
- an ethanol mixed solution was prepared by mixing ethanol 196 g, pure water 1 Og, and ammonia 1 Og, and the powder I2 was added to the mixed solution. After dispersing with an ultrasonic disperser for 5 minutes, 6 g of tetraorthosilicate (TE0S) was added while stirring with a stirrer, and reacted for 5 hours.
- TE0S tetraorthosilicate
- the slurry containing the silica film forming powder was repeatedly decanted and washed with sufficient alcohol.
- titania / silica-coated iron powder I3 For 20 g of titania / silica-coated iron powder I3, add 198.3 g of ethanol in advance. Was prepared by adding 22 g of titanium isopropoxide to the mixture, and dispersing the powder I3 in the liquid in a separable flask. g of pure water in 47.9 g of ethanol was added dropwise over 1 hour. After the addition, the reaction was carried out at room temperature for 4 hours. After the reaction, dilute and wash with sufficient ethanol, separate into solid and liquid, dry with a vacuum dryer at 110 ° C for 3 hours, and after drying, heat treat at 65 ° C for 30 minutes in a rotary tube furnace. After cooling, titania / silica-coated iron powder I4 was obtained.
- This 14 had a spectral reflection curve peak wavelength at 450 nm and was cyan.
- This I5 had a peak wavelength of a spectral reflection curve at 380 nm and 820 nm, and had valleys at 355 nm, 556 nm and 902 nm, and was magenta.
- the magnetization of the powder I5 at 10k0e was 14 O emu / g.
- Table 9 shows the film thicknesses of the first to sixth layers, the peak wavelength of the spectral reflection curve of the film-coated powder, the peak height (H), the half width (W), and the ratio (H / W).
- Pattern 1 was printed using PG10 manufactured by Riso Kagaku to obtain a printed matter PH for discrimination.
- the pattern of "B” was printed with the ink-like composition LH using PG10 manufactured by Riso Kagaku, and the periphery was printed using LI to obtain a composition for identification PI.
- the authenticity can be easily determined by visual inspection.
- spherical iron powder (trade name: HQ) manufactured by BAS F with a particle size of 1.8 ⁇ was selected.
- the coating layer, on the base particles, were selected as the alternate four layers of the S i 0 2 and T i O 2.
- the R flat value obtained by solving the following equation 1 is applied to the following equation 2 to obtain a wavelength of 430 nm light.
- the calculated value of the thickness of each coating film was determined so as to show the maximum reflection for c
- dj thickness of the j-th layer from the bottom
- the calculated film thickness of each coating film obtained by the above equations 1 and 2 is 60.3 nm for the first layer S i 0 2 film, 49.2 nm for the second layer T i 0 2 film, third layer S i 0 2 film 70. 6 nm, was 6 nm 43. Te fourth layer T i 0 2 film.
- SiO 2 films were formed on the selected base particles (spherical iron powder HQ manufactured by BASF) by changing the film forming reaction conditions.
- the SiO 2 film was formed by a metal alkoxide hydrolysis method described in International Patent Publication No. WO 96/28269.
- the eight first layer S i 0 2 film grain diameter correction film-coated powder was cut by focusing Ionbi beam (FIB) processing, to measure the actual thickness value (d M) from their cross-section with an electron microscope
- FIB Ionbi beam
- the wavelengths of the eight types of first-layer S i 0 2 film-coated powder for film particle diameter correction as the maximum absorption were measured with a spectrophotometer, and the value obtained by dividing the maximum absorption wavelength value by 4 was used as the optical film.
- the thickness value (nd) was used.
- Figure 2 shows the eight first layer S i 0 actual thickness value of 2 film grain diameter correction film-coated powder (d M) relationship curve of the optical thickness value (nd) (dashed line) .
- the solid line shows the calculated value of the relationship between the actual film thickness value (d M ) and the optical film thickness value (nd) obtained by the above equations 1 and 2.
- the three types of second-layer T io 2 film particle size correction film-coated powders were processed by focused ion beam (FIB) processing in the same manner as the first-layer S io 2 film particle size measurement film-coated powder.
- the actual film thickness (d M ) was measured with an electron microscope from those cross sections, and the results were as shown in Table 11 below.
- the second-layer TiO 2 film was formed in the same manner as the first-layer Sio 2 film by the hydrolysis of the metal alkoxide described in International Patent Publication WO96 / 28269. Performed by the decomposition method.
- the third-layer S i O 2 film and the fourth-layer T i 0 2 film are also used for particle size correction similarly to the first-layer S i 0 2 film and the second-layer T i 0 2 film. Preparation of film-coated powder, correction of spectrophotometric characteristics corresponding to the calculated film thickness, and film formation were performed.
- FIG. 4 show the calculated values of the spectrophotometric curves of the third-layer SiO 2 film and the fourth-layer TiO 2 film.
- FIG. 5 shows the actual spectrophotometric curve of the powder after coating with each coating film, and shows that after coating the fourth Ti 0 2 film, the relative reflectance at 1.40 nm was 1.45. A reflection peak was obtained. This was a value higher than the relative reflectance (1.31) of the reflection peak obtained at 43 O nm after coating the second layer TiO 2 film.
- the relative reflectance is a value obtained by dividing the reflectance from the coating powder by the reflectance from the base particles.
- Equation 1 Based on the substrate particles (spherical iron powder HQ manufactured by BAS F) and the coating layer structure selected in Example 10 above, solving Equation 1 above shows that the R nat value shows the maximum reflection for a wavelength of 43 Onm light.
- the thickness of each coating film and the calculated value of the spectrophotometric curve were obtained. Thickness calculated values of the coating film, 54. 5 nm of the first layer S i 0 2 film, the second layer T I_ ⁇ 2 film Te 46. 0 nm, the third layer S i 0 2 film in 6 3. 3 nm, it was 4 7. 5 nm Te fourth layer T i 0 2 film.
- the calculated values of the relative reflectance of each coating film are as shown in FIG.
- each coating film was formed so as to have a reflection pattern or a peak shown in FIG.
- it carried out similarly to the said Example 1 by the hydrolysis method of the metal alkoxide of international patent publication WO96 / 28269.
- Figure actual spectrophotometric curve after coating each coating film in S io 2 one T i 0 2 alternating 4-layer-coated powder that was created by the film thickness design based on multilayer coating plate members as described above 7 Shown in In result, the relative reflectance of the reflection peak obtained in 43 O nm after the fourth layer T i 0 2 film coating is 1. 33, 430 nm after the second-layer T i 0 2 film-coated The relative reflectance of the obtained reflection peak was the same (1.33), and the relative reflectance did not increase even if the number of films increased.
- Example 10 a method similar to that of Example 1 was used, except that the preparation of the particle-coated film coating powder and the correction of the spectrophotometric characteristics corresponding to the calculated film thickness were not performed.
- Each coating film was formed such that the coating film showed the reflection valley or peak shown in FIG. 1, and a four-layer Sio 2 -Tio 2 alternating coating powder was prepared.
- the relative reflectance of the reflection peak obtained at 430 nm of the obtained powder was 1.248, which was smaller than the powder (relative reflectance of 1.45) obtained in Example 1. .
- each coating film having the calculated film thickness value obtained in Comparative Example 1 was formed on a flat plate base having the same material as the used base particles (spherical iron powder HQ manufactured by BAS F).
- the 2— Tio 2 alternating 4-layer coated plate had a relative reflectance of 1.255 at 430 nm. Therefore, in the first embodiment, four layers of S i 0 2 -T i O 2 alternating four layers formed without performing the preparation of the particle coating powder for particle diameter correction and the correction of the spectral photometric characteristic corresponding to the calculated film thickness. It was also found that the relative reflectance of the coated powder was smaller than that of a multilayer-coated flat plate in which a coating layer of the same structure was provided on a base material of the same material.
- the film-coated powder of the present invention, the coating composition, and the coated material are based on a proprietary technique, and the number of films is preferably increased to two or more to increase the film thickness so that the peak in the reflection spectrum can be obtained.
- the powder of the present application having a specific thickness which has been appropriately designed for the thickness of each coating film so as to increase the reflection intensity of the specific wavelength light, has a brighter color and a higher saturation than before. A variety of colors such as large color shifts are emitted accurately.
- Such powders are useful in many fields of industry, for example in automotive coatings, decorative coatings, plastic pigment coloring, paints, printing inks, and the like.
- Such a film-coated powder of the present invention, a coating composition, and a coated material of the present invention can be used to prevent forgery secret documents such as banknotes, checks, check cards, credit cards, income stamps, stamps, railway and air tickets, and telephones. It is also useful for cards, lottery tickets, gift certificates, travel and identification cards.
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Description
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Priority Applications (8)
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PCT/JP2002/002434 WO2003076526A1 (fr) | 2002-03-14 | 2002-03-14 | Poudre enrobee, composition de revetement et articles revetus |
CA002477956A CA2477956A1 (en) | 2002-03-14 | 2002-03-14 | Coated powder, coating composition, and coated article |
AU2002238907A AU2002238907A1 (en) | 2002-03-14 | 2002-03-14 | Coated powder, coating composition, and coated article |
EA200401205A EA200401205A1 (ru) | 2002-03-14 | 2002-03-14 | Порошок с плёночным покрытием, кроющая композиция и покрытый материал |
KR10-2004-7014420A KR20050002857A (ko) | 2002-03-14 | 2002-03-14 | 막 피복된 분말, 도료 조성물 및 도포물 |
EP02705198.6A EP1484365B1 (en) | 2002-03-14 | 2002-03-14 | Coated powder, coating composition and coated article |
CNA02828934XA CN1628155A (zh) | 2002-03-14 | 2002-03-14 | 薄膜涂布的粉末、涂料组合物和涂布材料 |
US10/507,349 US20050208303A1 (en) | 2002-03-14 | 2004-03-14 | Coated powder, coating composition, and coated article |
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JPWO2016006664A1 (ja) * | 2014-07-10 | 2017-04-27 | 日本ペイントホールディングス株式会社 | 赤外反射性顔料及び赤外反射性塗料組成物 |
JP2018536733A (ja) * | 2015-11-11 | 2018-12-13 | Cqv株式会社Cqv Co., Ltd. | 中空構造を有する光沢顔料及びその製造方法 |
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- 2002-03-14 EA EA200401205A patent/EA200401205A1/ru unknown
- 2002-03-14 CN CNA02828934XA patent/CN1628155A/zh active Pending
- 2002-03-14 EP EP02705198.6A patent/EP1484365B1/en not_active Expired - Lifetime
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US7507222B2 (en) | 1998-04-09 | 2009-03-24 | Becton, Dickinson And Company | Method and apparatus for shielding the tip of a catheter introducer needle |
JPWO2016006664A1 (ja) * | 2014-07-10 | 2017-04-27 | 日本ペイントホールディングス株式会社 | 赤外反射性顔料及び赤外反射性塗料組成物 |
US10131790B2 (en) | 2014-07-10 | 2018-11-20 | Nippon Paint Holdings Co., Ltd. | Infrared-reflective pigment and infrared-reflective coating composition |
JP2018536733A (ja) * | 2015-11-11 | 2018-12-13 | Cqv株式会社Cqv Co., Ltd. | 中空構造を有する光沢顔料及びその製造方法 |
US10836912B2 (en) | 2015-11-11 | 2020-11-17 | Cqv Co., Ltd | Glossy pigment having hollow structure and method for producing same |
Also Published As
Publication number | Publication date |
---|---|
AU2002238907A1 (en) | 2003-09-22 |
CA2477956A1 (en) | 2003-09-18 |
US20050208303A1 (en) | 2005-09-22 |
EP1484365A4 (en) | 2012-07-04 |
EP1484365B1 (en) | 2020-04-29 |
KR20050002857A (ko) | 2005-01-10 |
EP1484365A1 (en) | 2004-12-08 |
EA200401205A1 (ru) | 2005-04-28 |
CN1628155A (zh) | 2005-06-15 |
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