WO2003042121A1 - Composition de couleur ceramique et pate de couleur ceramique - Google Patents
Composition de couleur ceramique et pate de couleur ceramique Download PDFInfo
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- WO2003042121A1 WO2003042121A1 PCT/JP2002/011945 JP0211945W WO03042121A1 WO 2003042121 A1 WO2003042121 A1 WO 2003042121A1 JP 0211945 W JP0211945 W JP 0211945W WO 03042121 A1 WO03042121 A1 WO 03042121A1
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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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
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- 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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/02—Surface treatment of glass, not in the form of fibres or filaments, by coating with glass
- C03C17/04—Surface treatment of glass, not in the form of fibres or filaments, by coating with glass by fritting glass powder
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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
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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
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/44—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the composition of the continuous phase
- C03C2217/45—Inorganic continuous phases
- C03C2217/452—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
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
- C03C2217/465—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase having a specific shape
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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
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
- C03C2217/48—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase having a specific function
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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
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
- C03C2217/48—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase having a specific function
- C03C2217/485—Pigments
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
- C04B2235/3234—Titanates, not containing zirconia
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3409—Boron oxide, borates, boric acids, or oxide forming salts thereof, e.g. borax
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/38—Non-oxide ceramic constituents or additives
- C04B2235/3804—Borides
- C04B2235/3813—Refractory metal borides
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/52—Constituents or additives characterised by their shapes
- C04B2235/5208—Fibers
- C04B2235/526—Fibers characterised by the length of the fibers
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/52—Constituents or additives characterised by their shapes
- C04B2235/5208—Fibers
- C04B2235/5264—Fibers characterised by the diameter of the fibers
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/52—Constituents or additives characterised by their shapes
- C04B2235/5276—Whiskers, spindles, needles or pins
Definitions
- the present invention relates to a ceramic color composition suitable for reuse as a glass raw material after use, and a method for producing a glass plate with a ceramic color layer suitable for reuse.
- a ceramic color layer which is an opaque coloring layer, is formed on the inner periphery of the window glass of an automobile.
- This ceramic color layer is interposed between the urethane sealant that holds the window glass from the inside of the vehicle at the periphery and the window glass that is held, thereby preventing the ultraviolet sealant from deteriorating due to ultraviolet rays.
- terminals such as heating wires provided on the inner peripheral portion of the window glass are not visible from the outside of the vehicle.
- 'One layer is a ceramic color composition containing low-melting glass powder and heat-resistant pigment powder as essential components, pasted, coated on a glass plate, dried and baked, and then baked on the glass plate. Glass plates with ceramic layers are manufactured.
- the heat-resistant pigment powder is usually black.
- a glass plate with a ceramic color layer used as a window glass of an automobile is conventionally crushed when the automobile is scrapped, and is disposed of by landfilling.
- a manganese compound is disclosed in Japanese Patent Application Laid-Open No. 2000-5005772, and a manganese compound is disclosed in Japanese Patent Application Laid-Open No. 2000-89189.
- the bit Kusubaiaito structure (F e, M n) 2 0 3 respectively used as heat resistant pigment powder Ceramic color compositions are disclosed.
- glass plates with ceramic color layers using these ceramic color compositions have low sintering properties of the ceramic color layer, or ceramics viewed through the glass plate from the side where the ceramic color layer is not baked. The color layer looks whitish, etc.
- An object of the present invention is to provide a reusable ceramic color composition, a ceramic color paste, and a method for producing a reusable glass plate with a ceramic color layer, which solves such a problem. Disclosure of the invention
- the present invention consists essentially of 60-85% low melting glass powder, 15-40% heat-resistant pigment powder, 0-15% heat-resistant whiskers and 0-15% refractory powder in terms of mass percentage.
- E 3 0 4 reference content of 6 (hereinafter referred to as Fe 3 0 4 content.)
- C F e 1 to 35% Mn_ ⁇ 2 reference content of M n hereinafter Mn0 2 content referred.)
- C M n There are 1 to 24% (:.
- a method for producing a glass plate with a ceramic color layer wherein the ceramic color composition is applied to a glass plate and fired to form a ceramic color layer baked on the glass plate It is called a board manufacturing method.
- the coloring component contained in the ceramic color layer reduces the visible light transmittance of the glass plate manufactured in the glass melting furnace. Quality troubles may occur.
- the present inventors have studied this point as follows, and have reached the present invention.
- the raw material for a glass melting furnace usually consists of a batch prepared from industrial raw materials such as silica sand and cullet, and the batch ratio is 0.2 or more.
- a glass plate used for an automobile window glass or the like is manufactured by a float method. That is, the molten glass is formed into a glass ribbon in a float bath, gradually cooled, cut into a desired length, and both ends are cut off to form a glass plate.
- a peripheral portion or the like is further cut off as necessary to obtain a desired shape.
- factory cullet Is reused.
- the factory cullet ratio c 1 is greater than 0.4 for molten glass.
- a glass sheet with a single layer of ceramics collected from a scrapped vehicle is used as a power retlet (hereinafter, such cullet collected from a scrapped vehicle is referred to as a scrapped car cullet)
- the mass of the ceramic color layer baked on the window glass used in automobiles is 30-35 g per vehicle, and the mass of the window glass is 0.0007-0.001. Equivalent to.
- the content x ′ of X in the automotive window glass is at most 0,1 ⁇ ⁇ ⁇ .
- the factory power reticle generated for the first time after the use of the scrap car cullet contains the scrap vehicle power let at a ratio of c2.
- cl is 0.4 as described above, c 2 is 0.24 when the scrap car cullet recovery rate is 60%. Is 0.4.
- ⁇ ′ is a change in the optical properties of the automotive window glass.
- the present inventors have studied the coloring components having a large extinction coefficient among the coloring components considered as X, that is, Fe, Mn, Cr, Cu, Ni, Co, V, Ti, and Se.
- the change in visible light transmittance Tv of green soda-lime silica glass (5 mm thick) containing 0.5% of Fe 2 ⁇ 3 as a coloring agent must be 1% or less.
- ⁇ V is JIS R3106 3.4 “Visible light transmittance and visible light reflectance of single-pane glass” except that standard light A specified in JISZ87203.2 is used as standard light. Calculation ”.
- C r 2 0 3 content simply C r 2 0 3, abbreviated as equal, (C r 2 0 3 Z 8. 5 + CuO / 2 3 + N i 0/3. 3 + C oO / O. 7 1 + V 2 0 5/56 + S e /. 45) ( hereinafter referred to as Q ) was determined to be 1% or less, which led to the present invention.
- the content in the present invention is represented by mass percentage unless otherwise specified.
- Fe 3 F 4 standard content of Fe in the present invention? 6? 6 3 is a content determined as exist at 0 4 forms. The same applies to the contents of other components. Further, in the present specification, for example, the F e 3 0 4 content referred to C F e, or simply abbreviated as F e 3 0 4. The same applies to the contents of other components.
- the F e 3 0 4 content in the ceramic color composition of the present invention which corresponds to F e 3 ⁇ 4 content in sintered body obtained by firing the composition,
- the composition Is determined using the fluorescent X-ray method. The same applies to the contents of other components.
- the low melting point glass in this specification is a glass having a softening point T s of 650 ° C. or less. T s is preferably at most 600 ° C.
- the ceramic color composition of the present invention is usually kneaded with a binder such as ethyl cellulose and an organic solvent such as monoterpineol to form a paste, coated on a glass plate, dried and fired, soda lime silica. It is a ceramic color layer baked on a glass plate.
- the paste is the ceramic paste of the present invention.
- the coating is performed by screen printing, the drying is performed at 80-140 ° C. for 5-15 minutes, and the baking is performed at 630-700 for 3-8 minutes. .
- the glass plate When the ceramic color composition of the present invention is baked on a glass plate by the above-mentioned firing, the glass plate may be simultaneously bent and formed into a curved glass plate for laminated glass. After the bend forming, the curved glass sheet is quenched and strengthened continuously.It may be used as a curved glass sheet. ⁇ Curved glass sheet for laminated glass, tempered. Bending of curved glass sheet is typically 630 ° C X 4 each. In this condition, the ceramic color composition of the present invention is baked on a glass plate at the same time as bending to form a ceramic color layer.
- the method for manufacturing a glass plate with a ceramic color layer described here is a method for manufacturing a glass plate of the present invention.
- Fe 3 0 4 content in the ceramic color composition of the present invention Mn0 2 content, C r 2 0 3 content, CuO content, N i O content, CoO content, V 2 0 5 containing Yuryou,
- the Se content will be described below.
- F e 3 0 4 content ceramic color layer of opacity is reduced is less than 1%. It is preferably at least 3%, more preferably at least 5%. If it exceeds 35%, the fluidity during firing decreases. It is preferably at most 24%, more preferably at most 15%.
- Mn0 2 content opacity of the ceramic color layer is lowered less than 1%. It is preferably at least 4%, more preferably at least 7%. If it exceeds 24%, the fluidity during firing decreases. It is preferably at most 19%, more preferably at most 15%.
- F e 3 0 4 + Mn0 2 is 5-30%. If it is less than 5%, the opacity of the ceramic color layer may be reduced. It is more preferably at least 10%, particularly preferably at least 15%. If it exceeds 30%, the fluidity during firing may decrease. It is more preferably at most 27%, particularly preferably at most 24%.
- C r 2 0 3 content and CuO content may be either 0 percent, C r 2 0 3 + CuO must be at least 1%. If it is less than 1%, the ceramic color layer seen through the glass plate looks whitish from the side where the ceramic color layer is not baked (hereinafter referred to as the non-printing side). It is preferably at least 3%. Further, Cr 2 O 3 + CuO is preferably at most 10%, more preferably at most 7%.
- N i O content, CoO content, V 2 0 5 content and S e content may be 0% with each, may not be 0%.
- Fe 3 0 4 content in the ceramic color composition of the present invention Mn0 2 content, C r 2 ⁇ 3 content, CuO content, N I_ ⁇ content, C o 0 content, V 2 0 5 containing Yes Having described the amount and the Se content, the content of typical components other than these will be described below. That, S i 0 2: 5 ⁇ 31% , B i 2 0 3: 0 ⁇ 52%, ZnO:.
- Low-melting glass powder is an essential component for baking the ceramic color layer on the glass plate. If it is less than 60%, baking will be insufficient. It is preferably at least 65%. If it exceeds 85%, the content of the heat-resistant pigment powder becomes small. Preferably it is 80% or less.
- T s of the low melting point glass powder is 540 ⁇ 580 ° C
- average linear expansion coefficient a in 50 to 350 ° C is preferably respectively a 50X 10 7 Z ° C ⁇ 130 X 10- 7 / ° C.
- T S 730 ° C
- ⁇ 87 X 10- 7 / ° C.
- the low-melting glass powder is preferably one that crystallizes during firing. If it does not crystallize during firing, the mold release property may be reduced.
- Bismuth silicate crystals or zinc silicate crystals are exemplified as the crystals that precipitate during the calcination, and the temperature Tc of the crystallization peak observed when these crystals precipitate in differential thermal analysis is 580 to 650 ° C. Preferably, there is.
- Low melting glass powder is essentially based on the following ingredients:
- Components other than the above components may be contained within a range that does not impair the object of the present invention, but the total content of these components is preferably 5% or less, more preferably 3% or less.
- the PbO content of the low-melting glass is preferably set to 0%.
- a content of a component of 0% or more means that the component is not essential.
- ZnO: 0 45% means “ZnO is not essential but 45% May be contained up to this point ”.
- the low-melting glass powder is essentially Si 2 : 20 40% Bi 2 O o: 15 45% ZnO: 0 25% B 0 3: 0 ⁇ : L 5%, T I_ ⁇ 2: 0 ⁇ 5%, Z r 0 2: 0 ⁇ 5%, Al 2 O 3: 0-5%, MgO: 0 ⁇ 5%, C aO: 0 ⁇ 5 %, B aO: 0 ⁇ 5%, L i 2 O: 0 ⁇ 1 0%, Na 2 O: 0 ⁇ 10%, K 2 O: 0 ⁇ 10%, Ce_ ⁇ 2: 0 ⁇ 3%, F: More preferably, it is comprised between 0 and 2%.
- a low-melting glass powder is essentially, S I_ ⁇ 2: 10 ⁇ 45%, B i 2 0 3: 15 ⁇ 40%, Z ⁇ : 25 ultra - 45%, B 2 ⁇ 3: 0 ⁇ 10%, T I_ ⁇ 2: 0 ⁇ 5%, Z r 0 2: 0 ⁇ 5%, A 1 2 0 3: 0 ⁇ 5%, MgO: 0 ⁇ 5% , CaO: 0 ⁇ 5%, B aO : 0 ⁇ 5%, L i 2 O: 0 ⁇ 10%, Na 2 O: 0 ⁇ 10%, K 2 O: 0 ⁇ 7%, Ce_ ⁇ 2: 0 3%, F: 0 to 2%, and more preferably precipitates crystals when fired at 650 to 680 ° C.
- a low-melting glass powder is essentially, S i O 2: 10 ⁇ 38% , B i 2 O 3 50 ⁇ 75%, B 2 0 3: 0 ⁇ 8%, T i 0 2: 0 ⁇ ; L 2%, Z r0 2: 0 ⁇ : L 0%, A 12 0 3: 0 ⁇ 10%, B aO: 0 ⁇ 12%, L i 2 O: 0 ⁇ 10%, Na 2 ⁇ : 0 ⁇ 10%, K 2 ⁇ : 0 ⁇ 5%, C e 0 2 : 0 ⁇ 3%, F: 0 ⁇ 2%, consists, 650 One that precipitates a crystal when fired at 680 ° C.
- the heat-resistant pigment powder is a component that blocks ultraviolet rays and also blocks visible light, and is essential. If it is less than 15%, the ultraviolet ray shielding effect or the visible light shielding effect becomes insufficient. Preferably it is more than 18%. If it exceeds 40%, baking will be insufficient. It is preferably at most 35%.
- the heat-resistant pigment powder preferably contains at least one of Cr and Cu, Fe and Mn. More preferably, it is a black pigment powder which is a powder containing copper-chromium double oxide, iron-manganese double oxide, magnetite or the like as a main component or a mixture of these powders. It is particularly preferable to contain a copper-chromium-manganese double oxide powder and an iron-manganese double oxide powder.
- a heat-resistant whisker is not essential, but may be contained up to 15% in order to suppress a decrease in the strength of the glass plate due to the formation of the ceramic color layer. If it exceeds 15%, the fluidity at the time of baking will decrease, and baking will be insufficient. It is preferably at most 10%, more preferably at most 7%.
- the heat-resistant whisker has a melting point of 700 ° C or higher, a fiber diameter of 0.1 to 10 m, a fiber length of 0.5 to 100 mm, a fiber diameter of 0.001 to 2 and an inorganic whisker. It is. Typically, the melting point is 1000 ° C or higher, the fiber diameter is 0.5 to 5 m, the fiber length is 5 to 50 ⁇ m, and the fiber diameter / fiber length is 0.01 to 0.1.
- the heat-resistant whisker is at least one inorganic substance selected from the group consisting of aluminum borate, ⁇ -alumina, potassium titanate, zinc oxide, magnesium oxide, magnesium borate, basic magnesium sulfate, and titanium diboride. Whiskers, and more preferably aluminum borate.
- the refractory powder is not essential, but may be contained up to 15% in order to adjust the expansion coefficient of the fired body. If it exceeds 15%, the fluidity at the time of firing decreases and baking becomes insufficient. . It is preferably at most 10%, more preferably at most 5%.
- the refractory powder is a refractory powder having a melting point of 700 ° C or more and is not an inorganic whisker, and a boride powder having a melting point of 700 ° C or more and not an inorganic whisker.
- Nitride powder or silicide powder, and oxide powder such as ⁇ -alumina, quartz, zircon, cordierite, j3-eucryptite, forsterite, mullite, and steatite. None are exemplified.
- the ceramic color composition of the present invention consists essentially of the above components, but may contain other components as long as the purpose of the present invention is not impaired.
- the other components are essentially of the above components, but may contain other components as long as the purpose of the present invention is not impaired.
- the total content of the other components is preferably 5% or less, more preferably 3% or less.
- the flake glass was pulverized with a pole mill to obtain a mass average particle diameter D 5 .
- the obtained glass powders A, B, and C were subjected to differential thermal analysis in which the temperature was raised to 800 ° C. in 10 ° C.Z minutes, and the softening point T s (unit: C) and the crystallization peak temperature T c (unit: ° C) was measured, also a differential thermal dilatometer used in alpha (unit: 1 0- 7 Z ° C) was measured. No crystallization peak was observed for glass powder A.
- Glass powder A was used in Examples 1 to 5
- glass powder B was used in Examples 6 and 7
- glass powder C was used in Examples 8 and 9, respectively.
- Example 3 only 42-313A was used.
- Examples 4, 7, and 9 only manganese dioxide reagent powder manufactured by Kanto Chemical Co., Ltd. was used.
- Example 5 only manganese carbonate reagent powder manufactured by Junsei Chemical Co., Ltd. was used.
- Alporex YS10 manufactured by Shikoku Chemicals was used as the aluminum borate whisker.
- the composition of ALBOREX YS 10 is 9 A 1 2 0 3 ⁇ 2 B 2 0 3, the fiber diameter of 0.. 5 to 5 m, fiber length. 5 to 50 ⁇ m, fiber diameter Z fiber length 0. 01 to 1.
- composition of the mass percentage of the ceramic color compositions are shown in the column of up to Fe 3 0 4 ⁇ Mo0 3 of Table 2.
- the composition was calculated from the composition of the glass powder, the X-ray fluorescence analysis composition of the heat-resistant pigment powder, and the composition of the aluminum borate power.
- Examples 1, 2, 6, and 8 are Examples, and Examples 3, 4, 5, 7, and 9 are Comparative Examples.
- paste 20 parts by mass of a 0; -terpineol solution obtained by dissolving 10% of ethyl cellulose in terms of percentage by mass was added, kneaded, and homogeneously dispersed by a three-roll mill to obtain a ceramic color.
- Paste hereinafter simply called paste.
- the paste thus obtained was screen-printed on the entire surface of a 3.5 mm thick, lOcmXIOcm, soda-lime silica glass plate and dried.
- the glass plate coated with the paste was baked at 630 ° C for Examples 1 to 5 and 670 ° C for Examples 6 to 9 for 4 minutes, and then cooled to room temperature, with a ceramic layer.
- a glass plate was obtained.
- the color difference ⁇ E and sinterability of this glass plate with a ceramic color layer were measured or evaluated as follows. The results are shown in the table.
- ⁇ is preferably 1.0 or less. If it exceeds 1.0, the ceramic color layer may look whitish when viewed from the non-printing side. More preferably, it is 0.5 or less.
- the sinterability of the ceramic color layer is good, the ceramic color layer viewed from the non-printing surface side does not look whitish, and the raw material of the glass melting furnace is
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- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
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- Glass Compositions (AREA)
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP02781794A EP1452498A4 (en) | 2001-11-15 | 2002-11-15 | CERAMIC COLOR COMPOSITION AND CERAMIC COLOR PASTE |
US10/793,858 US6835680B2 (en) | 2001-11-15 | 2004-03-08 | Ceramic color composition and ceramic color paste |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2001350072A JP2003146696A (ja) | 2001-11-15 | 2001-11-15 | セラミックカラー組成物およびセラミックカラーペースト |
JP2001-350072 | 2001-11-15 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/793,858 Continuation US6835680B2 (en) | 2001-11-15 | 2004-03-08 | Ceramic color composition and ceramic color paste |
Publications (1)
Publication Number | Publication Date |
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WO2003042121A1 true WO2003042121A1 (fr) | 2003-05-22 |
Family
ID=19162649
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2002/011945 WO2003042121A1 (fr) | 2001-11-15 | 2002-11-15 | Composition de couleur ceramique et pate de couleur ceramique |
Country Status (4)
Country | Link |
---|---|
US (1) | US6835680B2 (ja) |
EP (1) | EP1452498A4 (ja) |
JP (1) | JP2003146696A (ja) |
WO (1) | WO2003042121A1 (ja) |
Cited By (1)
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CN112334423A (zh) * | 2018-07-24 | 2021-02-05 | 庄信万丰股份有限公司 | 颗粒混合物、套盒、墨、方法和制品 |
Families Citing this family (14)
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US6936556B2 (en) | 2002-05-15 | 2005-08-30 | Ferro Corporation | Durable glass enamel composition |
AU2003239417A1 (en) | 2002-05-15 | 2003-12-02 | Ferro Corporation | Durable glass enamel composition |
US20050288166A1 (en) * | 2004-06-24 | 2005-12-29 | Jun-Kyu Cha | Lead-free black ceramic composition for filter and filter formed using the same |
KR101190921B1 (ko) * | 2004-07-22 | 2012-10-12 | 도레이 카부시키가이샤 | 감광성 페이스트 및 디스플레이 패널용 부재의 제조 방법 |
CN101371195A (zh) * | 2006-01-12 | 2009-02-18 | 东丽株式会社 | 感光性组合物、显示器构件及其制造方法 |
US20140179506A1 (en) * | 2012-12-24 | 2014-06-26 | King Abdul Aziz City for Science and Technology (KACST) | Self glazed ceramic/glass composite and method for manufacturing the same |
CN105143131A (zh) * | 2013-05-28 | 2015-12-09 | 日本电气硝子株式会社 | 复合粉末、复合粉末糊剂及带着色层的玻璃板 |
CN103787579B (zh) * | 2014-02-18 | 2016-04-20 | 南通向阳光学元件有限公司 | 一种绿色光学玻璃组合物 |
CN103787578B (zh) * | 2014-02-18 | 2016-04-20 | 南通向阳光学元件有限公司 | 一种黑色光学玻璃组合物 |
JP7196906B2 (ja) * | 2018-04-11 | 2022-12-27 | 昭栄化学工業株式会社 | 誘電体磁器組成物及びセラミック電子部品 |
WO2020247193A1 (en) * | 2019-06-05 | 2020-12-10 | Ferro Corporation | Colored glass frits and related methods for laser marking applications |
CN111302647A (zh) * | 2020-03-30 | 2020-06-19 | 山东省淄博市博山长虹陶瓷装饰材料厂 | 不含锌硼的玻璃颜料熔剂及其制备方法和应用 |
CN112551905A (zh) * | 2020-12-27 | 2021-03-26 | 西安赛尔电子材料科技有限公司 | 防爆锂原电池盖组及其封接玻璃的制备方法和封接工艺 |
CN114590999B (zh) * | 2022-01-20 | 2023-05-05 | 广西科技大学 | 一种低熔点无铅玻璃粉及其制备方法 |
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WO1998025864A1 (fr) * | 1996-12-12 | 1998-06-18 | Saint-Gobain Vitrage | Procede d'emaillage de substrats en verre, composition d'email utilisee et produits obtenus |
JP2000154037A (ja) * | 1998-11-13 | 2000-06-06 | Asahi Glass Co Ltd | セラミックカラー組成物 |
EP1078895A2 (de) * | 1999-08-21 | 2001-02-28 | dmc2 Degussa Metals Catalysts Cerdec AG | Verfahren zur Herstellung schwarzer recyclingfähiger Glasemails, Glasfarbe hierfür und damit emaillierte Glassubstrate |
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DE4401657C2 (de) * | 1994-01-21 | 1996-02-08 | Dieter Kuestner | Glasrecyclingverträgliche Pigmente und deren Verwendung |
DE19525658C1 (de) * | 1995-07-14 | 1996-11-28 | Sekurit Saint Gobain Deutsch | Einbrennbare Druckpaste zum Bedrucken von Glasoberflächen und Verfahren zur Herstellung der Druckpaste |
DE59802213D1 (de) * | 1997-08-08 | 2002-01-10 | Dmc2 Degussa Metals Catalysts | Bleifreie Glaszusammensetzungen mit niedrigem Schmelzpunkt |
US6287996B1 (en) * | 1998-09-14 | 2001-09-11 | Asahi Glass Company Ltd. | Ceramic color composition and process for producing a curved glass plate |
FR2796063B1 (fr) * | 1999-07-08 | 2001-08-17 | Saint Gobain Vitrage | Nouvelle composition d'email noir, recyclable, comprenant du zinc, procede de fabrication et produits emailles obtenus |
-
2001
- 2001-11-15 JP JP2001350072A patent/JP2003146696A/ja not_active Withdrawn
-
2002
- 2002-11-15 EP EP02781794A patent/EP1452498A4/en not_active Withdrawn
- 2002-11-15 WO PCT/JP2002/011945 patent/WO2003042121A1/ja not_active Application Discontinuation
-
2004
- 2004-03-08 US US10/793,858 patent/US6835680B2/en not_active Expired - Fee Related
Patent Citations (3)
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WO1998025864A1 (fr) * | 1996-12-12 | 1998-06-18 | Saint-Gobain Vitrage | Procede d'emaillage de substrats en verre, composition d'email utilisee et produits obtenus |
JP2000154037A (ja) * | 1998-11-13 | 2000-06-06 | Asahi Glass Co Ltd | セラミックカラー組成物 |
EP1078895A2 (de) * | 1999-08-21 | 2001-02-28 | dmc2 Degussa Metals Catalysts Cerdec AG | Verfahren zur Herstellung schwarzer recyclingfähiger Glasemails, Glasfarbe hierfür und damit emaillierte Glassubstrate |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112334423A (zh) * | 2018-07-24 | 2021-02-05 | 庄信万丰股份有限公司 | 颗粒混合物、套盒、墨、方法和制品 |
CN112334423B (zh) * | 2018-07-24 | 2022-07-15 | 庄信万丰先进玻璃技术有限责任公司 | 颗粒混合物、套盒、墨、方法和制品 |
Also Published As
Publication number | Publication date |
---|---|
EP1452498A4 (en) | 2006-07-26 |
JP2003146696A (ja) | 2003-05-21 |
EP1452498A1 (en) | 2004-09-01 |
US20040171472A1 (en) | 2004-09-02 |
US6835680B2 (en) | 2004-12-28 |
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