WO2017169905A1 - セラミック装飾用の赤絵具 - Google Patents
セラミック装飾用の赤絵具 Download PDFInfo
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- WO2017169905A1 WO2017169905A1 PCT/JP2017/010934 JP2017010934W WO2017169905A1 WO 2017169905 A1 WO2017169905 A1 WO 2017169905A1 JP 2017010934 W JP2017010934 W JP 2017010934W WO 2017169905 A1 WO2017169905 A1 WO 2017169905A1
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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
- C09D5/06—Artists' paints
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
- C03C14/004—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix the non-glass component being in the form of particles or flakes
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
- C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
- C03C8/18—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing free metals
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5022—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with vitreous materials
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/86—Glazes; Cold glazes
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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
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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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
- C09D5/004—Reflecting paints; Signal paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—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
- 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
- C09D7/66—Additives characterised by particle size
- C09D7/67—Particle size smaller than 100 nm
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/80—Optical properties, e.g. transparency or reflexibility
- C04B2111/82—Coloured materials
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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
- C08K2003/0806—Silver
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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
- C08K2003/0831—Gold
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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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
Definitions
- the present invention relates to a ceramic decorative red paint. Specifically, the present invention relates to a red paint containing nano gold (Au) particles and nano silver (Ag) particles as a red colorant. Note that this application claims priority based on Japanese Patent Application No. 2016-068160 filed on Mar. 30, 2016, the entire contents of which are incorporated herein by reference. Yes.
- a dough is first prepared by kneading and forming a raw material such as kaolin, silica sand, and feldspar, which is a raw material, and drying and unbaking.
- glaze and paint are applied to the surface of the dough and fired with painting.
- red is a color that is in high demand for national flags, corporate logos, characters, and Christmas-related items.
- a red coloring material contained in a red paint a cadmium-based material such as selenium and cadmium red has been widely used since it can produce a vivid red color.
- the use of selenium and cadmium red tends to be limited due to the harmful effects of cadmium.
- the present invention has been made in view of these circumstances, and an object thereof is to provide a red paint for ceramic decoration (coloring) capable of vivid red coloring.
- a red paint for ceramic decoration having a glass matrix and a red coloring material and a protective material mixed in the glass matrix.
- the red colorant includes nano gold particles and nano silver particles.
- the protective material includes nano silica particles.
- Nano gold particles absorb green to light blue light and exhibit a bluish red (red purple) color called “malon”.
- the nano silver particles absorb blue light and exhibit a yellow color.
- red colorant blue light contained in “malon” derived from nano gold particles can be absorbed by the nano silver particles.
- a bright red color can be realized.
- dispersing the red coloring material in the glass matrix together with the protective material it becomes difficult for the red coloring material to dissolve in the glass matrix at the time of baking with painting, and it is possible to stably realize a clear red color development. .
- the “nanoparticle” has an arithmetic average value (D50 particle size) of an equivalent circle diameter based on observation with an electron microscope such as a transmission electron microscope (TEM) of 1 to 100 nm. Means things.
- TEM transmission electron microscope
- ceramic refers to all non-metallic inorganic materials unless otherwise specified. For example, ceramic materials and glass materials are typical examples included in the ceramic of the present specification.
- Patent Document 1 discloses a red glaze containing nano copper particles. According to Patent Document 1, red coloring is realized by painting and baking the red glaze in an oxidizing atmosphere. However, when the nano copper particles described in Patent Document 1 are baked in an oxidizing atmosphere (for example, in an air atmosphere), copper is oxidized and copper (II) oxide is generated. Therefore, the use of the red glaze, insufficient brightness or yellowness (e.g. L * a * b * L * values and b * values in color system) becomes the color tone sank dark red escutcheon. Therefore, the above red glaze was not a substitute for selenium / cadmium red, which exhibits a bright red color, for example.
- the proportion of the nano gold particles is 0.05 parts by volume or more and 0.5 parts by volume. Below the volume. Thereby, the a * value in the red direction in the L * a * b * color system can be improved, and the red color development can be enhanced. Further, the brightness L * value in the L * a * b * color system is improved, and a bright and vivid color can be suitably realized. Furthermore, it can suppress that a red paint becomes expensive too much, and can suppress cost.
- the ratio of the nano silver particles is 0.05 parts by volume or more and 0.4. Below the volume. Thereby, the b * value in the yellow direction in the L * a * b * color system is improved, and the blueness of the nanogold particles can be suppressed at a high level. Therefore, sharper red color development can be realized. Moreover, it can suppress that a red paint becomes expensive too much, and can suppress cost.
- the volume of the protective material is 20 times or more the volume of the red coloring material. This makes it difficult for the red colorant to be further taken into the glass matrix at the time of baking with painting, and the red fading is better suppressed. As a result, excellent red color developability can be achieved at a higher level.
- the ratio of the protective material is 10% by volume or more and 40% by volume or less when the total of the glass matrix and the protective material is 100% by volume.
- a ceramic product having a red decorative portion includes glass, gold, and silver.
- the red decorative part has the following conditions in the L * a * b * color system based on Japan Industrial Standard JIS Z8729 (2004): L * value is 35 to 70; a * value Is 20 or more; b * value is 15 or more.
- the red decorative portion has a 45 ° specular glossiness of 70% or more based on Japan Industrial Standard JIS Z8741 (1997).
- FIG. 1 is a flowchart for explaining a method of manufacturing a red paint according to an embodiment of the present invention.
- FIG. 2 is a matrix table showing the relationship between the content of the red colorant and the lightness and chromaticity of the L * a * b * color system.
- the red paint disclosed here is a red paint for forming a red decorative portion on the ceramic by applying it to the surface of the ceramic as an object to be decorated and baking with painting.
- the red paint has a glass matrix, a red coloring material and a protective material dispersed in the glass matrix, and the red coloring material includes nano gold (Au) particles and nano silver (Ag) particles.
- the protective material includes nano silica particles. Accordingly, the other properties are not particularly limited, and can be arbitrarily determined in light of various standards. For example, various components can be blended or the composition thereof can be changed. Hereinafter, each component will be described in order.
- the glass matrix has a matrix property that disperses the red coloring material and the protective material.
- a red coloring material and a protective material are mixed in the glass matrix.
- the glass component, the red colorant component, and the protective material component are typically sintered integrally to form a sintered body.
- the glass matrix is a component that functions as an inorganic binder for the red colorant, and functions to enhance the bonding between the red colorant and the ceramic that is the object to be decorated.
- the linear thermal expansion coefficient of the glass constituting the glass matrix (average linear expansion coefficient measured in the temperature range from 25 ° C. to 500 ° C. using a thermomechanical analyzer; the same applies hereinafter) is not particularly limited, It is good that it is equivalent to ceramics.
- the linear thermal expansion coefficient of the glass is preferably about (thermal expansion coefficient ⁇ 2 ⁇ 10 ⁇ 6 ) K ⁇ 1 of the object to be decorated.
- the linear thermal expansion coefficient of the glass may be, for example, 4.0 ⁇ 10 ⁇ 6 K ⁇ 1 to 8.0 ⁇ 10 ⁇ 6 K ⁇ 1 .
- the glass transition point of the glass constituting the glass matrix (Tg value based on differential scanning calorimetry. The same shall apply hereinafter) is not particularly limited.
- the glass transition point is preferably about 400 to 1500 ° C.
- the glass transition point is preferably about 900 to 1300 ° C. for use in undercoating or sink-in.
- the glass transition point is preferably about 500 to 900 ° C.
- SiO 2 -RO represents an oxide of a Group 2 element, for example, MgO, CaO, SrO, BaO. The same)) system glass, SiO 2 —RO—R 2 O (where R 2 O is an oxide of an alkali metal element such as Li 2 O, Na 2 O, K 2 O, Rb 2 O, Cs 2 O, Fr 2 O) In particular, Li 2 O.
- These glasses may contain one or more components in addition to the main constituent components appearing in the above designation.
- the glass may be a crystallized glass containing crystals in addition to a general amorphous glass.
- SiO 2 accounts for more than half (50 mol%) when the entire glass is 100 mol%.
- the glass transition temperature the higher the proportion of SiO 2 is high.
- it may reduce the proportion of SiO 2 generally below 80 mol%.
- lowering the glass transition point in terms of improving the meltability of the glass it is effective to add a component such as RO and R 2 O, B 2 O 3 .
- RO accounts for 15 to 35 mol% when the entire glass is 100 mol%.
- R 2 O occupies 0 to 5 mol% when the entire glass is 100 mol%.
- the glass is composed of a multicomponent system having four or more components (for example, five or more components).
- a red decorative portion is required to have sufficient acid resistance against acidic food and sufficient alkali resistance against an alkaline detergent.
- it is effective to add, for example, components such as Al 2 O 3 , ZnO, and CaO at a ratio of, for example, 1 mol% or more in addition to the main constituent components appearing in the above names.
- the chemical durability of a red decoration part can be improved more.
- wear resistance can also be improved.
- the glass does not substantially contain components that may adversely affect the human body or the environment, such as arsenic components, lead components, and cadmium components.
- these components are not added positively (incorporation as an unavoidable impurity is acceptable) in applications used for tableware decoration.
- the ratio of the glass matrix in the red paint is not particularly limited. From the viewpoint of increasing the bonding property with the ceramic to be decorated, when the entire red paint is 100% by volume, the ratio of the glass matrix is generally 50% by volume or more, typically 60% by volume or more. It is good in it being 70 volume% or more. Further, from the viewpoint of improving the red color developability, when the entire red paint is 100% by volume, the ratio of the glass matrix is generally 95% by volume or less, typically 90% by volume or less, for example 80% by volume or less. It is good to be. For the same reason, when the total of the glass matrix and the protective material is 100% by volume, the ratio of the glass matrix is approximately 50% by volume or more, typically 60% by volume or more, for example 70% by volume or more. Thus, it is generally 95% by volume or less, typically 90% by volume or less, for example, 80% by volume or less.
- the red colorant is a component that imparts red color to the surface of the ceramic that is the object to be decorated.
- the red colorant is mixed in the glass matrix together with the protective material.
- the red coloring material and the protective material may exist in an independent state, for example, the protective material may gather around the red coloring material and exist in a lump shape.
- the red coloring material includes nano gold particles and nano silver particles as nano metal particles.
- Nano metal particles have their own optical characteristics (for example, a strong light absorption band) in the ultraviolet to visible region due to surface plasmon resonance (SPR).
- nano gold (Au) particles absorb light having a wavelength around 530 nm (green to light blue light) and exhibit a bluish red color called “malon” (red purple).
- nano silver (Ag) particles absorb yellow light (blue light) having a wavelength near 420 nm and exhibit a yellow color. For this reason, when nano gold particles and nano silver particles are used in combination, the bluish wavelength of the nano gold particles is absorbed by the nano silver particles, and a bright red color is realized.
- the nano gold particles and the nano silver particles may be in the form of single particles or in an alloy state.
- the red colorant contains, for example, nanometal particles other than gold and silver at a volume ratio of 1/10 or less of the total volume of nanogold particles and nanosilver particles, as long as the effects of the present invention are not significantly impaired. You may go out.
- Each of the nano gold particles and the nano silver particles has a D50 particle size of nanometer size (approximately 1 to 100 nm) in consideration of the surface plasmon resonance.
- the effect of surface plasmon resonance of nanometal particles can vary with particle size. By appropriately adjusting the particle size to the nanometer size, the effect of surface plasmon resonance can be enjoyed better.
- the D50 particle size of the nanogold particles and nanosilver particles is 5 nm or more, typically 10 nm or more, for example, 15 nm or more.
- the nanogold particles and nanosilver particles each have a D50 particle size of approximately 80 nm or less, typically 50 nm or less, such as 30 nm or less.
- the absorbance at a specific wavelength of the nanometal particles can be increased, and a good red color can be realized with a small amount of addition. In addition, it is possible to realize a precise decoration with little color unevenness.
- the mixing ratio of nano gold particles and nano silver particles is not particularly limited because it can be influenced by, for example, the particle size and particle size distribution of nano metal particles.
- the volume ratio there may be more nano gold particles or more nano silver particles.
- the proportion of the red coloring material in the red paint is not particularly limited. From the viewpoint of improving red color development and cost, the ratio of the red colorant is approximately 0.1% by volume or more, for example, 0.15% by volume or more when the entire red paint is 100% by volume. In general, it is good to be 1% by volume or less, typically 0.8% by volume or less, for example 0.7% by volume or less. For the same reason, when the total of the glass matrix and the protective material is 100 parts by volume, the ratio of the red coloring material is approximately 0.1 parts by volume or more, for example, 0.15 parts by volume or more, and approximately 1 It may be less than or equal to volume parts, typically less than or equal to 0.8 volume parts, such as less than or equal to 0.7 volume parts. In a preferred embodiment, the volume of the red colorant is approximately 1/100 to 1/200, for example, 1/120 to 1/180 of the volume of the glass matrix. Thereby, uniform red color development can be realized stably.
- the proportion of nanogold particles is generally 0.05 parts by volume or more, preferably 0.1 parts by volume or more, for example, 0.1 part by volume. 11 parts by volume or more.
- the ratio of nano gold particles is approximately 0.5 parts by volume or less, typically 0.45 parts by volume or less.
- the ratio of the nano gold particles is set to a predetermined value or less, in the L * a * b * color system, the lightness L * value can be improved, and a bright and vivid color can be better realized. Further, the cost can be kept low.
- the ratio of the nanosilver particles is generally 0.05 parts by volume or more, preferably 0.1 parts by volume or more, for example, 0.1 part by volume. 11 parts by volume or more.
- the proportion of nano silver particles is generally about 0.4 parts by volume or less, preferably 0.35 parts by volume or less, for example 0.32 parts by volume or less.
- the protective material is a component for suppressing the fading of the red colorant during baking with painting and enhancing the red color developability. That is, the protective material has a melting point higher than the baking temperature with painting described later. For this reason, a red coloring material (nano metal) and glass become difficult to contact at the time of baking with painting by including a protective material in a red paint. By this, it can suppress that a red coloring material will be taken in as a structural component of glass, in other words, a red coloring material melt
- the protective material is mixed in the glass matrix together with the red coloring material.
- the protective material may be in a state separate from the red colorant, or may be in a state of being attached, bonded, or coordinated to the surface of the red colorant, for example.
- the protective material contains nano silica particles.
- Silica increases transparency when sintered. Therefore, there is an effect of enhancing the color developability of the red decorative portion or increasing the glossiness. Further, since silica is commercially available at a relatively low price, it is preferable from the viewpoint of availability and cost.
- the protective material may contain nanoceramic particles other than nanosilica particles, for example, in a volume ratio smaller than that of nanosilica particles. Specific examples include nano zirconia particles, nano alumina particles, and nano titania particles.
- the D50 particle size of the protective material is nanometer size (approximately 1 to 100 nm).
- the D50 particle size of the protective material (typically nanosilica particles) is typically the same as or smaller than the D50 particle size of the nanometal particles.
- the protective material has a D50 particle size of approximately 50 nm or less, typically 30 nm or less, such as 20 nm or less.
- the volume of the protective material is approximately 5 times or more, typically 10 times or more, preferably 20 times or more, for example, 30 times or more, of the volume of the red coloring material.
- the volume of the protective material is approximately 90 times or less, typically 80 times or less, preferably 70 times or less, such as 60 times or less, more preferably 50 times the volume of the red coloring material. It is as follows. As a result, it is possible to realize a red decorative portion having a better appearance (glossiness, brightness, and color tone).
- the ratio of protective material in the red paint is not particularly limited. From the viewpoint of improving the red color developability, when the total amount of red paint is 100% by volume, the ratio of the protective material is preferably about 10% by volume or more, for example, 20% by volume or more. Further, from the viewpoint of enhancing glossiness and brightness, when the entire red paint is taken as 100% by volume, the proportion of the protective material is preferably about 40% by volume or less, for example, 30% by volume or less. For the same reason, when the total of the glass matrix and the protective material is 100% by volume, the ratio of the protective material is approximately 10% by volume or more, for example, 20% by volume or more, and approximately 40% by volume or less, for example, It is good in it being 30 volume% or less.
- the red paint disclosed here may be composed of the above-described three components (glass, red coloring material, protective material), and, for example, 100% by volume of the entire red paint as long as the effects of the present invention are not significantly impaired. In the range of less than about 10% by volume, other components may be optionally included as appropriate. Examples of additional components include, for example, organic binders, reaction accelerators, surfactants, dispersants, thickeners, pH adjusters, preservatives, antifoaming agents, plasticizers, stabilizers, antioxidants, and the like. Is exemplified.
- the red paint is substantially free of components that can adversely affect the human body and the environment, such as arsenic components, lead components, and cadmium components (mixing them as unavoidable impurities is acceptable. ). In particular, it is preferable not to include these components in applications used for decorating tableware.
- the red paint disclosed here can be adjusted to any form depending on the application.
- a cullet shape, a powder shape, a frit shape, a pellet shape, a plate shape, a paste shape, and the like can be used.
- a solvent for example, an aqueous solvent
- a solvent may be added to the red paint to adjust it to a paste form.
- the method for producing such a red paint is not particularly limited.
- the red paint is manufactured by adding glass frit to a mixture of a red coloring material and a protective material, further mixing, drying, integrally sintering, and then pulverizing. be able to.
- each process is demonstrated in detail, referring the flowchart of FIG.
- the manufacturing method shown in FIG. 1 includes the following steps: (Step S1) A red coloring material and a protective material are mixed by a wet method to prepare a liquid first mixture; (Step S2) Mixing glass frit to prepare a second mixture; (Step S3) Heat-treating the second mixture to obtain a sintered body in which a red coloring material and a protective material are mixed in a glass matrix. (Step S4) crushing the sintered body.
- the red paint of this embodiment can be manufactured by a simple process of mixing and heat treatment. Therefore, for example, it is simpler than the production method in which a process of forming a silica film on the surface of the nanometal particles is essential, and is preferable from the viewpoint of workability and mass productivity.
- a red coloring material and a protective material are mixed.
- the red colorant at least nano gold particles and nano silver particles are prepared.
- a protective material at least nano silica particles are prepared. Since nanoparticles are highly cohesive, they are typically marketed in the form of a dispersion in which the particles are stabilized in a dispersion solvent. Therefore, in the present embodiment, the dispersion of each nanoparticle is weighed and mixed so that the nanogold particles, nanosilver particles, and nanosilica particles have a predetermined volume ratio.
- the mixing operation can be performed using, for example, a magnetic stirrer or ultrasonic waves. In this way, a liquid first mixture is prepared.
- step S2 glass frit is mixed with the liquid first mixture at a predetermined ratio.
- a highly homogenous mixture can be obtained by mixing the first mixture and the glass frit by a wet method. In this way, a liquid second mixture is prepared.
- the second mixture is heat-treated.
- the dispersion medium is first removed to some extent by drying in a temperature range of 100 ° C. or lower.
- this is heated at a temperature equal to or higher than the glass transition point of the glass frit to be integrally sintered.
- the sintering temperature is preferably set to approximately the glass transition point +0 to 300 ° C.
- the sintering temperature may be set to about 800 to 900 ° C.
- the sintering time is usually about 0.1 to several hours.
- the atmosphere during sintering may be an air atmosphere, an oxidizing atmosphere, an inert gas atmosphere, or the like.
- the sintered body is pulverized (can be crushed) and / or classified to adjust to a desired size or size.
- the pulverization operation can be performed using, for example, a vibration mill, a planetary mill, a stirring lightning machine, or the like.
- the shape and size of the red paint are not particularly limited, but from the viewpoint of handleability and the like, the average particle diameter based on, for example, the laser diffraction / light scattering method is approximately 10 ⁇ m or less, typically 0.1 to 10 ⁇ m, for example, 0 It is preferable to set the thickness to about 5 to 5 ⁇ m.
- the red paint obtained in this way is used to decorate the ceramic surface as an object to be decorated.
- the decoration work can be performed by applying the red paint to the surface of the ceramic and baking it at a predetermined temperature.
- red paint is applied to the ceramic surface and then painted at a high temperature of about 1200 to 1400 ° C. Baking is good.
- red paint is applied to the ceramic surface, followed by baking with painting at an intermediate temperature of about 700 to 1000 ° C. Good.
- the red paint of this embodiment can obtain a particularly good red color by the above-mentioned medium temperature baking.
- the baking with painting after applying the red paint can typically be performed in an air atmosphere (under an oxidizing atmosphere).
- dredged sand cupric oxide
- the red paint disclosed here exhibits a red color when fired in an air atmosphere, there is an advantage that a facility for maintaining a reducing atmosphere is unnecessary and it is easy to use.
- a ceramic product having a red decorative portion can be obtained.
- the “ceramic product” here includes ceramics, porcelain, earthenware, stoneware, glass and the like. Specific products include, for example, tableware, ornaments, various tiles, sanitary ware, tiles, bricks, clay pipes, and ceramic pipes.
- the red decorative part of ceramic products is a fired body containing at least glass, gold and silver.
- the red decoration part of this embodiment has realized the unique vivid red color development.
- the appearance (color tone and glossiness) of this red decorative part can further enhance the aesthetics and luxury of ceramics, leading to the provision of products with high customer satisfaction.
- the color tone of the red decorative portion of this embodiment is as follows in the L * a * b * color system based on JIS Z8729 (2004):
- the L * value is 35 to 70 (preferably 35 to 55);
- a * value is 20 or more (preferably 30 or more, for example 50 or less);
- B * value is 15 or more (preferably 20 or more, for example 40 or less);
- Can be suitably satisfied By setting the lightness L * value to a predetermined value or more, it is possible to realize bright and vivid colors.
- by setting the lightness L * value to be equal to or less than a predetermined value it is possible to realize deep and warm colors.
- a * value in the red direction is set to be equal to or greater than a predetermined value, it is possible to improve red color development and achieve a sharp and clear color.
- setting the b * value in the yellow direction to a predetermined value or more, in other words, by suppressing the -b * value in the blue direction to be small, for example, it is possible to suppress a purple-to-bluish color development such as “malon”. Thus, a bright red color can be realized.
- the glossiness of the red decorative portion of the present embodiment can satisfy, for example, a 45 degree specular glossiness of 70% or more, preferably 80% or more, particularly 90% or more based on JIS Z8741 (1997). As a result, when the light is irradiated, the red decorative portion is radiated and the glossiness is improved. In addition, the smoothness of the surface is increased, and a beautiful appearance full of luxury can be realized.
- nano gold particles and nano silver particles were prepared as red coloring materials, and the color tone was examined by changing the content ratios thereof.
- a nanogold particle dispersion (commercial product) having a D50 particle size of 20 nm a nanosilver particle dispersion (commercial product) having a D50 particle size of 20 nm, and a nanosilica particle having a D50 particle size of 20 nm.
- the dispersion liquid (commercial product) was mixed to obtain a first mixed liquid.
- a glass frit having a composition shown in Table 1 glass transition point: 640 ° C.
- the second mixed solution was dried in an oven and then heat-treated at a temperature of 800 to 900 ° C. for 30 minutes in an air atmosphere to obtain a sintered body.
- the obtained sintered body was pulverized with an Ishikawa stirring lightning pulverizer and then pulverized in order with a vibration mill and a planetary mill to produce a powdery red paint having an average particle size of 0.5 to 5 ⁇ m.
- the first mixed liquid and the second mixed liquid are 80% by volume of glass and 20% by volume of silica as a protective material in the state of red paint, and the total of glass and silica (100 parts by volume)
- the nano gold particle (Au) and nano silver particle (Ag) as a red coloring material may be contained in the ratio (volume part: parts by volume) shown in Table 2.
- each of the red paints prepared above was applied to the surface of a ceramic (test piece), and was fired with painting at 700 to 900 ° C. in an air atmosphere (under an oxidizing atmosphere) to obtain a ceramic having a red decorative part. And about the red decoration part, the lightness (L * ) and chromaticity (a * , b * ) of L * a * b * color system based on JISZ8729 (2004) using a spectrophotometer made by Konica Minolta ) was measured. The results are shown in the corresponding column of Table 2. Note that the “determination” column in Table 2 shows the determination results based on the determination criterion (1) in Table 3.
- FIG. 2 is a matrix table showing the relationship between the content of the red colorant and the lightness and chromaticity of the L * a * b * color system.
- Table 2 and FIG. 2 by using the red coloring material of Examples 1 to 8 containing nano gold particles and nano silver particles, the red decoration having a good chromaticity (a * , b * ) and vivid color development could be realized.
- the red paint of Examples 2 to 8 in which the ratio of the nano gold particles and the nano silver particles is 0.32 parts by volume or less with respect to the total of the glass matrix and the protective material, the brightness (L * ) Improved, and bright and vivid colors could be better realized.
- nano gold particles and nano silver particles were prepared as red coloring materials, and the color tone was examined by changing the content ratios thereof.
- glass and a protective material are contained in the ratio shown in Table 4 in a red paint, and with respect to the sum total (100 volume part) of glass and a silica.
- a red paint was obtained in the same manner as in I above, except that the preparation was made so that 0.3 volume part of nano gold particles as a red colorant and 0.2 volume part of nano silver particles were contained.
- the red decoration part was formed using the said red paint, and "appearance (color tone and glossiness)" was measured.
- the color tone measurement method is the same as that described in I.S. It is the same.
- the glossiness was measured using a gloss meter made by Nippon Denshoku Industries Co., Ltd. according to JIS Z8741 (1997).
- Table 5 shows the criteria for determining “color tone” and “glossiness”, and the determination result is shown in the corresponding column of Table 4.
- the color tone judgment criteria shown in Table 5 are the same as those in Test Example I.3. It is the same as the standard of double circle in. Therefore, in the color tone column of Table 4, those that satisfy the standard are indicated as “E (Excellent)”. In the glossiness column of Table 4, asterisks (*) are given to those not satisfying the criteria of Table 5. Further, the comprehensive judgment of Table 4 is judged as “E (Excellent)” when the color tone is “E” and the glossiness is 90% or more, and when the color tone is “E” and the glossiness is 80% or more, “ G (Good) ".
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Abstract
Description
なお、本出願は、2016年3月30日に出願された日本国特許出願2016-068160号に基づく優先権を主張しており、その出願の全内容は本明細書中に参照として組み入れられている。
セラミックの装飾において、赤色は、国旗や企業のロゴ、キャラクター、クリスマス関連などで需要の高い色である。赤絵具に含まれる赤色着色材としては、鮮やかな赤色発色が可能であることから、従来、セレン・カドミレッド等のカドミウム系の材料が汎用されてきた。しかし、セレン・カドミレッドは、カドミウムの有害性からその使用が制限される傾向にある。
また、本明細書において「セラミック」とは、特に言及しない限り、非金属無機材料全般をいう。例えば陶磁器材料やガラス材料などは本明細書のセラミックに包含される典型例である。
好適な一態様において、上記赤色装飾部は、日本工業規格(Japan Industrial Standard)JIS Z8741(1997年)に基づく45度鏡面光沢度が70%以上である。
ここに開示される赤絵具は、被装飾物としてのセラミックの表面に付与して画付焼成することにより、当該セラミックに赤色装飾部を形成するための赤絵具である。この赤絵具は、ガラスマトリックスと、該ガラスマトリックス中に分散している赤色着色材と保護材とを有し、上記赤色着色材がナノ金(Au)粒子とナノ銀(Ag)粒子とを含み、上記保護材がナノシリカ粒子を含んで構成されている。したがって、その他の性状については特に限定されず、種々の基準に照らして任意に決定し得、例えば種々の成分を配合したりその組成を変更したりすることができる。以下、各構成成分について順に説明する。
また、ガラス転移点を低下させてガラスの溶融性を向上する観点からは、ROやR2O、B2O3などの成分を添加することが有効である。一方で、これらの成分を多く含むほど、ガラスの熱膨張係数が大きくなる傾向にある。好適な一態様では、ガラス全体を100mol%としたときに、ROが15~35mol%を占めている。好適な他の一態様では、ガラス全体を100mol%としたときに、R2Oが0~5mol%を占めている。
好適な一態様では、ナノ金粒子およびナノ銀粒子のD50粒径が、それぞれ、5nm以上、典型的には10nm以上、例えば15nm以上である。好適な他の一態様では、ナノ金粒子およびナノ銀粒子のD50粒径が、それぞれ、概ね80nm以下、典型的には50nm以下、例えば30nm以下である。D50粒径を上記範囲とすることで、ナノ金属粒子の特定波長の吸光度が増大して、少量の添加で良好な赤色発色を実現することができる。また、色ムラの少ない、緻密な装飾を実現することができる。
好適な一態様では、赤色着色材の体積が、上記ガラスマトリックスの体積の概ね1/100~1/200、例えば1/120~1/180である。これにより、均質な赤色発色を安定的に実現することができる。
好適な他の一態様では、ガラスマトリックスと保護材との合計を100体積部としたときに、ナノ金粒子の割合が、概ね0.5体積部以下、典型的には0.45体積部以下、好ましくは0.35体積部以下、例えば0.32体積部以下である。ナノ金粒子の割合を所定値以下とすることで、L*a*b*表色系において、明度L*値を向上し、明るく鮮やかな色みをより良く実現することができる。また、コストを低く抑えることができる。
好適な他の一態様では、ガラスマトリックスと保護材との合計を100体積部としたときに、ナノ銀粒子の割合が、概ね0.4体積部以下、好ましくは0.35体積部以下、例えば0.32体積部以下である。ナノ銀粒子の割合を所定値以下とすることで、L*a*b*表色系において、明度L*値を向上し、明るく鮮やかな色みをより良く実現することができる。また、コストを低く抑えることができる。
好適な他の一態様では、保護材の体積が、上記赤色着色材の体積の概ね90倍以下、典型的には80倍以下、好ましくは70倍以下、例えば60倍以下、より好ましくは50倍以下である。これにより、外観(艶感や輝き、色調)がより良く高められた赤色装飾部を実現することができる。
このような赤絵具の製造方法は特に限定されないが、例えば、赤色着色材と保護材との混合物にガラスフリットを添加してさらに混合し、乾燥、一体焼結した後、粉砕することによって製造することができる。以下、図1のフローチャートを参照しつつ、各工程について詳しく説明する。
・L*値が35~70(好ましくは35~55)である;
・a*値が20以上(好ましくは30以上、例えば50以下)である;
・b*値が15以上(好ましくは20以上、例えば40以下)である;
を好適に満たし得る。
明度L*値を所定値以上とすることで、明るく鮮やかな色みを実現することができる。また、明度L*値を所定値以下とすることで、深みや温かみのある色みを実現することができる。また、赤方向のa*値を所定値以上とすることで、赤色発色性を高めて、シャープではっきりした色みを実現することができる。また、黄方向のb*値を所定値以上とすることで、換言すれば青方向の-b*値を小さく抑えることで、例えば「マロン」のように紫~青みがかった発色となることを抑制して、鮮やかな赤色発色を実現することができる。
この試験例では、赤色着色材としてナノ金粒子とナノ銀粒子とを用意し、これらの含有割合を変えることで色調に関する検討を行った。
具体的には、先ず、D50粒径が20nmのナノ金粒子の分散液(市販品)と、D50粒径が20nmのナノ銀粒子の分散液(市販品)とD50粒径が20nmのナノシリカ粒子の分散液(市販品)とを混合して、第1混合液を得た。次に、表1に示す組成のガラスフリット(ガラス転移点:640℃)を第1混合液に添加し、さらに混合することで、第2混合液を得た。この第2混合液をオーブンで乾燥した後、大気雰囲気において800~900℃の温度で30分間熱処理して、焼結体を得た。得られた焼結体を石川式撹拌雷潰機で解砕した後、振動ミルと遊星ミルで順に粉砕して、平均粒子径が0.5~5μmの粉末状の赤絵具を作製した。
なお、第1混合液及び第2混合液は、赤絵具の状態において、ガラスが80体積%、保護材としてのシリカが20体積%であり、かつ、ガラスとシリカとの合計(100体積部)に対して、赤色着色材としてのナノ金粒子(Au)とナノ銀粒子(Ag)とが表2に示す割合(体積部:parts by volume)で含まれるように調製した。
なお、表2の「判定」の欄には、表3の判定基準(1)に基づく判定結果を示している。表2の「判定1」の欄には、L*値の判定結果を示している。「判定1」の欄では、L*値が「◎」の場合に「E(Excellent)」と表記し、L*値が「〇」の場合に「G(Good)」と表記し、L*値が「×」の場合に「P(Poor)」と表記している。「判定2」の欄には、色度(a*、b*)の判定結果を示している。「判定2」の欄では、a*値、b*値がいずれも「◎」の場合に「E(Excellent)」と表記し、a*値、b*値のうち一方が「◎」でもう一方が「〇」である場合、あるいはa*値、b*値がいずれも「〇」の場合に「G(Good)」と表記し、a*値、b*値のうち少なくとも一方が「×」の場合に「P(Poor)」と表記している。
この試験例では、赤色着色材としてナノ金粒子とナノ銀粒子とを用意し、これらの含有割合を変えることで色調に関する検討を行った。ここでは、第1混合液及び第2混合液の状態において、赤絵具に、ガラスと保護材とが表4に示す割合で含まれ、かつ、ガラスとシリカとの合計(100体積部)に対して、赤色着色材としてのナノ金粒子が0.3体積部、ナノ銀粒子が0.2体積部含まれるように調製したこと以外は上記Iと同様に、赤絵具を得た。そして、当該赤絵具を用いて赤色装飾部を形成し、「外観(色調と艶感)」を測定した。
色調の測定方法は、上記I.と同様である。また、艶感の測定は、日本電色工業製の光沢度計を用い、JIS Z8741(1997年)に準拠して行った。表5には「色調」と「光沢度」の判定の基準を示し、判定結果を表4の該当欄に示す。なお、表5に示す色調の判定基準は、試験例I.における二重丸の基準と同じである。そのため、表4の色調の欄では、基準を満たしているものを「E(Excellent)」と示している。また、表4の光沢度の欄では、表5の基準に満たないものにアスタリスク(*)を付している。また、表4の総合判定は、色調が「E」かつ光沢度が90%以上の場合に「E(Excellent)」と判定し、色調が「E」かつ光沢度が80%以上の場合に「G(Good)」と判定した。
Claims (8)
- ガラスマトリックスと、該ガラスマトリックスに混在している赤色着色材および保護材と、を有し、
前記赤色着色材は、ナノ金粒子とナノ銀粒子とを含み、
前記保護材は、ナノシリカ粒子を含む、セラミック装飾用の赤絵具。 - 前記ナノ金粒子と前記ナノ銀粒子との体積比率が、ナノ金粒子:ナノ銀粒子=80:20~20:80である、請求項1に記載の赤絵具。
- 前記ガラスマトリックスと前記保護材との合計を100体積部としたときに、前記ナノ金粒子の割合が、0.05体積部以上0.5体積部以下である、請求項1又は2に記載の赤絵具。
- 前記ガラスマトリックスと前記保護材との合計を100体積部としたときに、前記ナノ銀粒子の割合が、0.05体積部以上0.4体積部以下である、請求項1~3のいずれか1項に記載の赤絵具。
- 前記保護材の体積が、前記赤色着色材の体積の20倍以上である、請求項1~4のいずれか1項に記載の赤絵具。
- 前記ガラスマトリックスと前記保護材との合計を100体積%としたときに、前記保護材の割合が、10体積%以上40体積%以下である、請求項1~5のいずれか1項に記載の赤絵具。
- 赤色装飾部を有するセラミックス製品であって、
前記赤色装飾部は、ガラスと金と銀とを含み、
前記赤色装飾部は、日本工業規格JIS Z8729(2004年)に基づくL*a*b*表色系において、以下の条件:
L*値が35~70である;
a*値が20以上である;
b*値が15以上である;
を満たす、セラミックス製品。 - 前記赤色装飾部は、日本工業規格JIS Z8741(1997年)に基づく45度鏡面光沢度が70%以上である、請求項7に記載のセラミックス製品。
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ES201890054A ES2698260B2 (es) | 2016-03-30 | 2017-03-17 | Pintura roja para decoracion de ceramica |
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US16/088,594 US11130872B2 (en) | 2016-03-30 | 2017-03-17 | Red paint for ceramic decoration |
CN201780020431.6A CN108884331B (zh) | 2016-03-30 | 2017-03-17 | 陶瓷装饰用的红色颜料 |
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ES2941332A1 (es) * | 2021-11-18 | 2023-05-19 | Univ Jaume I | Procedimiento de obtención in situ de un pigmento cerámico molturado |
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WO2018081000A1 (en) * | 2016-10-25 | 2018-05-03 | University Of Richmond | Gold nanoparticle in ceramic glaze |
CN112573827A (zh) * | 2020-12-15 | 2021-03-30 | 佛山市华意陶瓷颜料有限公司 | 一种低温镉硒红釉粉及其制备方法和应用 |
CN113234357B (zh) * | 2021-05-12 | 2023-05-05 | 闻涛 | 一种环保型高性能数码喷墨红色墨水的制备方法 |
CN113955940B (zh) * | 2021-11-24 | 2023-08-11 | 武汉市格勒特新材料有限公司 | 一种无色差抗菌抛釉陶瓷材料及其制备方法 |
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ES2698260A2 (es) | 2019-02-01 |
CN108884331A (zh) | 2018-11-23 |
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JP6732886B2 (ja) | 2020-07-29 |
JPWO2017169905A1 (ja) | 2019-02-07 |
ES2698260B2 (es) | 2019-11-21 |
US11674043B2 (en) | 2023-06-13 |
US11130872B2 (en) | 2021-09-28 |
US20210388214A1 (en) | 2021-12-16 |
CN108884331B (zh) | 2020-11-03 |
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