WO2013099514A1 - ブルッカイト型酸化チタン粉末およびその製造方法 - Google Patents
ブルッカイト型酸化チタン粉末およびその製造方法 Download PDFInfo
- Publication number
- WO2013099514A1 WO2013099514A1 PCT/JP2012/080943 JP2012080943W WO2013099514A1 WO 2013099514 A1 WO2013099514 A1 WO 2013099514A1 JP 2012080943 W JP2012080943 W JP 2012080943W WO 2013099514 A1 WO2013099514 A1 WO 2013099514A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- brookite
- titanium oxide
- oxide powder
- crystalline titanium
- powder
- Prior art date
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- C—CHEMISTRY; METALLURGY
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
- C01G23/0532—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing sulfate-containing salts
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/28—Titanium compounds
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K3/22—Oxides; Hydroxides of metals
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2002/30—Three-dimensional structures
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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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
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
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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
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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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.]
Definitions
- the present invention relates to a brookite type titanium oxide powder and a method for producing the same. According to the production method of the present invention, it is possible to obtain a highly pure brookite type titanium oxide powder very easily. Moreover, the brookite type titanium oxide obtained by this invention can be used conveniently for various uses from obtaining a solid powder with high purity.
- Titanium dioxide is naturally produced as a mineral of rutile, anatase or brookite. Of these, rutile mainly forms a deposit and is used as a raw material for metallic titanium. Anatas is universal but scattered and brookite is rare. Since these natural products contain niobium and tantalum, and there are problems such as lack of uniformity in particle size, all industrially used titanium dioxide is a synthetic product, and titanium-containing ores such as ilmenite are sulfated. The titanium hydroxide obtained by dissolution and further hydrolysis was heated at 500 ° C. or higher to obtain rutile and anatase. These titanium dioxides are mainly used as paint and cosmetic pigments, rubber and paper, and synthetic resin fillers.
- the refractive index of brookite shows a high value close to rutile, high whiteness, can cut ultraviolet rays, and has photoactive catalytic properties, so it is highly expected to be used in industrial fields such as cosmetics, paints and photocatalysts.
- Patent Document 1 amorphous titanium dioxide is added to an aqueous sodium hydroxide solution, and the molar ratio of Na 2 O / (Na 2 O + TiO 2 ) is 0.15 to 0.45 and TiO 2 is used.
- a method for producing brookite-type titanium oxide by adjusting the concentration to 140 g / L and hydrothermally treating the mixed solution at a temperature of 150 to 300 ° C. is disclosed.
- Patent Document 2 discloses a step of preparing a sol or gel of orthotitanic acid by hydrolyzing a titanium compound and peptization by adding hydrogen peroxide, and then cations and / or anions other than titanium.
- a method for producing titanium dioxide fine particles containing brookite-type crystals by a hydrothermal treatment in a temperature range of 350 ° C. has been proposed.
- Patent Document 3 anatase-type titanium oxide powder is added in an amount of 0.1 to 100: 1 in a weight ratio g of 10: 1 to 100: 1 by a ball mill exceeding the acceleration applied to the grinding medium colliding with the sample.
- a method for producing brookite-type titanium dioxide that is milled for 1 to 100 hours has also been proposed.
- Patent Document 4 discloses a brookite type characterized in that an aqueous solution containing a hydroxycarboxylic acid titanium complex is hydrothermally treated in a temperature range of 100 to 300 ° C. while maintaining the pH of the aqueous solution at 8 to 13.
- a method for producing titanium dioxide has been proposed, and it is described that nanoparticles having an average particle diameter of 5 to 300 nm can be obtained.
- Patent Document 1 describes that the presence or absence of mixed crystals can be confirmed by powder X-ray diffraction, and that the disclosed brookite-type titanium oxide is a single phase and does not include mixed crystals. There was no description of the particle size of the obtained product, and it was only disclosed that it could be pulverized as needed.
- Patent Document 2 brookite-type titanium oxide obtained by a conventionally known method of heating an alkaline aqueous solution has a large particle size of 100 ⁇ m or more and is non-uniform, dispersibility in a dispersion medium, transparency, and film-forming properties. However, the adhesion, coating hardness, abrasion resistance, etc.
- Patent Document 2 describes that fine titanium oxide particles having an average particle diameter of 1 to 600 nm can be obtained.
- the brookite-type titanium oxide shown in the examples was a mixed crystal having a content of 5 to 60%. That is, brookite-type titanium oxide having a single phase and an average particle size of 0.3 ⁇ m to 100 ⁇ m is not known, and it can be said that a method for producing such a particle has not been known.
- the above two methods require a hydrothermal reaction to react at a temperature higher than the boiling point by pressurizing in an alkaline liquid phase, which is dangerous and expensive to implement industrially. It was not a process that could be mass-produced at low cost.
- Patent Document 3 the method described in Patent Document 3 is not industrially easy, and the crystallinity of the resulting brookite crystals is not sufficient, so that it is difficult to say that the single-phase fine-particle brookite-type titanium oxide is obtained.
- Patent Document 4 there is a description that single-phase fine-particle brookite-type titanium oxide having an average particle diameter of 100 nm was obtained, but there was no description that other particle sizes were obtained. .
- “hydrothermal treatment” is indispensable as a production method, and it is also an industrially difficult production method because a large amount of ammonia needs to be used.
- An object of the present invention is to provide a high-purity fine particle brookite-type crystalline titanium oxide powder and a production method for industrially obtaining it.
- the present inventor has found that high-purity brookite-type crystalline titanium oxide powder can be easily obtained by heating titanium oxyoxalate, thereby completing the present invention. That is, the present invention is a high-purity brookite-type crystalline titanium oxide powder using titanium oxyoxalate as a raw material and a method for producing the same.
- the manufacturing method of the brookite type crystalline titanium oxide powder of the present invention is a manufacturing method that is simple and industrially simple in terms of equipment and conditions and operation.
- FIG. 1 The X-ray-diffraction figure measured with the powder X-ray-diffraction apparatus of the brookite type crystalline titanium oxide powder obtained in Example 1.
- FIG. 2 The X-ray-diffraction figure measured with the powder X-ray-diffraction apparatus of the brookite type crystalline titanium oxide powder obtained in Example 2.
- FIG. 3 The X-ray-diffraction figure measured with the powder X-ray-diffraction apparatus of the brookite type crystalline titanium oxide powder obtained in Example 3.
- FIG. 4 is a scanning electron micrograph of the brookite type crystalline titanium oxide powder obtained in Example 1.
- FIG. 4 is a scanning electron micrograph of the brookite type crystalline titanium oxide powder obtained in Example 1.
- brookite-type crystalline titanium oxide powder of the present invention (hereinafter also referred to simply as “brookite-type titanium oxide powder” or “brookite-type titanium oxide”) has an X-ray powder diffraction pattern of ASTM File No.
- Titanium dioxide having a crystal structure of brookite-type titanium oxide shown by 29-1360.
- the strongest diffraction peak of the brookite type titanium oxide crystal corresponding to the d value of 3.51 (100) appears at the diffraction angle 2 ⁇ 25.37 °.
- the purity of the brookite-type titanium oxide powder in the present invention can be confirmed by the powder X-ray diffraction pattern and the content of impurities, and the peak other than that attributed to the brookite-type titanium oxide powder is the maximum peak in the powder X-ray diffraction pattern.
- the X-ray diffraction intensity of a certain d value of 3.51 is preferably 0% or more and 10% or less, more preferably 0% or more and 5% or less, and further preferably 0%, that is, other peaks are observed. Is not.
- the purity (mass%) of brookite-type titanium oxide crystals since a standard substance of brookite-type titanium oxide crystals 100% is not available in the market, purity analysis by the standard addition method or the like is difficult. Therefore, in the present invention, the results of powder X-ray diffraction measurement are divided into X-ray diffraction intensity derived from brookite-type titanium oxide crystals and X-ray diffraction intensity of rutile, anatase, raw material titanium oxyoxalate, etc.
- the linear diffraction intensity ratio is defined as the mass ratio
- the purity is defined as the purity (mass%) with the entire crystal component being 100%.
- the X-ray diffraction intensity of d value 3.51 which is a characteristic diffraction peak of brookite-type titanium oxide powder, is 40 kv / 150 mA, which is a standard measurement condition, using CuK ⁇ rays.
- cps When expressed in terms of X-ray diffraction intensity cps when measured, it is preferably 200 cps or more, more preferably 500 cps or more. Moreover, it is preferable that it is 100,000 cps or less. If the X-ray diffraction intensity at a d value of 3.51 is 200 cps or more under these measurement conditions, the amorphous or other product is hardly mixed, and the purity of the brookite-type titanium oxide powder is high.
- the particle size of the brookite-type titanium oxide powder of the present invention is based on a general laser diffraction particle size distribution meter, and the median diameter calculated on a volume basis can be defined as a particle size representative of the powder. .
- the particle size of the brookite type titanium oxide powder of the present invention is preferably 0.3 to 40 ⁇ m in terms of median diameter, more preferably 0.5 to 40 ⁇ m, and further preferably 1.5 to 25 ⁇ m.
- a spherical powder can also be produced by using the production method of the present invention.
- the brookite-type titanium oxide crystal powder of the present invention is preferably spherical. It is difficult to control a sphere to be a perfect sphere. In SEM observation, the sphere includes those that are somewhat flat or have a “substantially spherical” shape with some surface irregularities. Other than the manufacturing method of the present invention described later, it is difficult to obtain a spherical shape, and the shape becomes an ellipsoidal to cylindrical shape, an annular shape, a crushed shape, an indeterminate shape, or the like. The classification of these shapes is obvious at a glance when observed with a scanning electron microscope (SEM). However, the definition of the sphere in the present invention is that it looks circular from any direction, and any point on the surface of the particle.
- the length of a line from a to a different point b is x
- the line connecting points a to b where x is the maximum value is the particle long axis
- points a to b where x is the minimum value When the line connecting the lines is defined as the particle short axis, in the group of particles, the ratio of the length of the particle short axis to the particle long axis is in the range of 0.5 to 1 and 100% or more of all the particles are 100%. % Or less.
- the ratio of the particle short axis to the particle long axis is greater than 0 and less than 0.5, an ellipsoid is formed, and when the end surface of the particle long axis has a plane area of 3 to 97 area% of the surface area, the shape is cylindrical. Define.
- the method for producing brookite-type crystalline titanium oxide powder of the present invention is also referred to as crystalline titanium oxyoxalate powder (hereinafter simply referred to as “titanium oxyoxalate”, “titanium oxyoxalate crystal”, or “titanium oxyoxalate powder”). And a heating step of heating the crystalline titanium oxyoxalate powder at a temperature of 550 ° C. to 820 ° C. Moreover, the brookite type crystalline titanium oxide powder of the present invention can be easily produced by the method for producing the brookite type crystalline titanium oxide powder of the present invention.
- the powder X-ray diffraction pattern of the titanium oxyoxalate crystal used in the present invention is ASTM File No. 48-1164, and the d value is 3.35 (100), 4.62 (90), 3.22 (78), 6.48 (65), 4.24 (62), 2.84. (45), 1.88 (44), 2.59 (36), 4.18 (26), and 7.76 (24).
- the X-ray diffraction intensity with a d value of 3.35 is preferably 3,000 cps or more.
- a titanium oxyoxalate having such a diffraction intensity is referred to as crystalline titanium oxyoxalate.
- the titanium oxyoxalate crystal is mixed with the raw material titanium oxyoxalate crystal, the chemical reactivity of the titanium oxyoxalate crystal is lowered. Therefore, the X-ray intensity indicating the titanium oxide crystal is preferably 20 cps or less.
- the method for producing crystalline titanium oxyoxalate in the preparation step may be a conventional method.
- a 0.1 mol / L aqueous solution of oxalic acid is mixed with a 1 mol / L aqueous solution of titanyl oxysulfate. By doing so, it can be obtained as a precipitate.
- the mixing order of oxalic acid and titanyl oxysulfate is not limited, and the titanyl oxysulfate aqueous solution may be dropped into the oxalic acid aqueous solution, the oxalic acid aqueous solution may be dropped into the titanyl oxysulfate aqueous solution, or simultaneously dropped into water.
- a preferable dropping temperature is 100 ° C. or lower, and more preferably 1 ° C. or higher and 80 ° C. or lower, which is excellent in operability and control degree of particle diameter.
- titanyl oxysulfate As a raw material for crystalline titanium oxyoxalate, it is preferable to use titanyl oxysulfate from the viewpoint that it is easily available and inexpensive, and can easily produce crystalline titanium oxyoxalate.
- the production method of the present invention preferably includes a step of mixing at least oxalic acid and titanyl oxysulfate as the preparation step, a step of mixing oxalic acid and titanyl oxysulfate, and oxalic acid and oxysulfate.
- Titanium oxyoxalate is easily crystallized by heating and aging after mixing the raw materials, and a preferable aging temperature is 50 ° C. to 100 ° C.
- the aging time is not particularly limited, but is preferably 0.5 to 48 hours, and more preferably 1 to 20 hours.
- the obtained titanium oxyoxalate suspension is washed with deionized water by a method such as repeating a ceramic filter or washing filtration, and washed with water until the electric conductivity of the filtrate becomes 0 ⁇ S (Siemens) or more and 500 ⁇ S or less. Then, since an impurity is removed, it is preferable.
- the particle size of titanium oxyoxalate used in the production method of the present invention is based on a general laser diffraction particle size distribution analyzer, and the median diameter calculated on a volume basis is defined as the particle size representative of powder. can do.
- the particle diameter of titanium oxyoxalate is preferably 0.1 to 40 ⁇ m in terms of median diameter, more preferably 0.3 to 30 ⁇ m, and further preferably 1.5 to 25 ⁇ m.
- the preferable brookite-type titanium oxide powder in the present invention preferably has a sulfur atom content (hereinafter also referred to as “sulfur content”) of 0.05 to 1.5 mass%.
- sulfur content a sulfur atom content
- Titanium oxide powder is usually known to be synthesized from sulfate as a raw material for titanium compounds, but derived from this sulfate, ordinary titanium oxide contains 2% by mass or more of sulfur as a sulfur atom. is doing. Although it is difficult to reduce the sulfur content, it can be reduced by the heat treatment of the production method of the present invention, and can be reduced to 1.5% by mass or less by heating at 600 ° C. or higher.
- the sulfur content is more preferably 1.0 to 0.07% by mass, still more preferably 0.7 to 0.09% by mass.
- the preferable heating temperature in the heating step is 600 ° C. or more and 810 ° C. or less. Preferably they are 650 degreeC or more and 810 degrees C or less, More preferably, they are 730 degreeC or more and 810 degrees C or less.
- a preferable heating time in the heating step is 0.5 hours or more and 48 hours or less, more preferably 1 hour or more and 20 hours or less, excluding the temperature raising time and the temperature lowering time.
- the heating furnace used for heating the titanium oxyoxalate is not limited, and an electric furnace, a gas furnace, or the like can be used. A furnace can also be used.
- a higher temperature rising rate when raising the temperature to the heating temperature is preferable because a brookite-type titanium oxide having a high purity can be obtained.
- a preferable temperature increase rate is 10 ° C./hour to 300 ° C./hour.
- a faster temperature-decreasing rate after the heat treatment is finished is preferable because brookite-type titanium oxide having a high purity can be obtained.
- a preferable temperature decreasing rate is between 10 ° C./hour and 300 ° C./hour. When the temperature is lowered by air cooling, it is difficult to make the temperature decrease rate constant, so the temperature decrease rate may change during the temperature decrease.
- the manufacturing method of this invention may include well-known processes other than having mentioned above. Examples thereof include a step of washing the obtained brookite type crystalline titanium oxide powder, and a step of drying the obtained brookite type crystalline titanium oxide powder or the washed brookite type crystalline titanium oxide powder. Further, after the heating step, the drying step, etc., when the obtained brookite-type crystalline titanium oxide particles partially adhered to each other to form secondary particles, the production method of the present invention was obtained. A step of crushing brookite-type crystalline titanium oxide to obtain brookite-type crystalline titanium oxide powder may be included.
- the usage form of the brookite-type titanium oxide powder of the present invention is not particularly limited, and can be appropriately mixed with other components or combined with other materials depending on the application.
- it can be used in various forms such as powder, powder-containing dispersion, powder-containing particles, powder-containing paint, powder-containing fiber, powder-containing paper, powder-containing plastic, powder-containing film, and powder-containing aerosol.
- the particle size of the brookite-type titanium oxide powder is within the preferred range of the present invention because aggregation is unlikely to occur and the dispersibility is good.
- the particle shape is spherical because dispersibility is further improved. In applications including a step of molding using a mold, if the particle shape is spherical, there is an effect that it is difficult to damage the mold.
- the brookite-type titanium oxide powder of the present invention can be mixed with various additives as necessary in order to improve kneading into a resin and other physical properties.
- additives such as zinc oxide and titanium oxide, inorganic ion exchangers such as zirconium phosphate and zeolite, dyes, antioxidants, light-resistant stabilizers, flame retardants, antistatic agents, foaming agents, impact-strengthening agents, Lubricants such as glass fibers, metal soaps, moisture-proofing agents and extenders, coupling agents, nucleating agents, fluidity improvers, deodorants, wood powder, antifungal agents, antifouling agents, rust preventives, metal powders, UV rays There are absorbers, ultraviolet screening agents, anti-allergens and the like.
- a photocatalytic resin composition can be easily obtained by blending the brookite crystalline titanium oxide powder of the present invention with a resin.
- the type of resin that can be used is not particularly limited, and may be any of a natural resin, a synthetic resin, and a semi-synthetic resin, and may be any of a thermoplastic resin and a thermosetting resin. Specific resins may be molding resins, fiber resins, and rubber-like resins.
- urea resin tetrafluoroethylene resin, unsaturated polyester resin, rayon, acetate, acrylic, polyvinyl alcohol, cupra, triacetate, vinylidene, etc.
- the photocatalytic fiber can also be produced by combining the brookite-type crystalline titanium oxide powder of the present invention with a natural fiber fiber.
- the blending ratio of the brookite-type crystalline titanium oxide powder of the present invention in the photocatalytic resin composition is preferably 0.1 to 50 parts by weight, and 0.5 to 20 parts by weight with respect to 100 parts by weight of the photocatalytic resin composition. More preferred. When the amount is 0.1 parts by weight or more, the photocatalytic resin composition has sufficient photocatalytic properties, and when it is 50 parts by weight or less, the resin physical properties are excellent.
- Any known method can be adopted as a processing method for blending the brookite-type crystalline titanium oxide powder of the present invention with a resin to obtain a resin molded product.
- a processing method for blending the brookite-type crystalline titanium oxide powder of the present invention with a resin to obtain a resin molded product For example, (1) using an additive for easily adhering brookite-type titanium oxide powder and resin or a dispersant for improving the dispersibility of brookite-type titanium oxide powder, (2) A method of directly mixing with a mixer, (2) A method of mixing as described above, forming into a pellet form with an extrusion molding machine, and then blending the molded product into a pellet-like resin, (3) Brookite type titanium oxide A method of blending a pellet-shaped molded product into a pellet-shaped resin after being molded into a high-concentration pellet using wax, (4) Paste form in which brookite-type titanium oxide is dispersed and mixed in a highly viscous liquid such as polyol There
- any known processing technique and machine can be used according to the characteristics of various resins, and mixing, mixing or mixing while heating and pressurizing or depressurizing at an appropriate temperature or pressure. They can be easily prepared by a kneading method, and their specific operation may be performed by a conventional method. Various operations such as a lump, sponge, film, sheet, thread or pipe, or a composite thereof may be used. Can be molded into form.
- the use form of the brookite-type crystalline titanium oxide powder of the present invention is not particularly limited, and is not limited to blending into a resin molded product or a polymer compound. Depending on the application where photocatalytic properties are required, it can be appropriately mixed with other components or combined with other materials. For example, it can be used in various forms such as powder, liquid dispersion, granular, aerosol, or liquid.
- the brookite-type crystalline titanium oxide powder of the present invention is used in various fields where deodorization, mold prevention, algae and antibacterial properties are required due to its photocatalytic activity, that is, electrical appliances, kitchen products, textile products, residential building materials products. It can be used as toiletry products, paper products, toys, leather products, stationery and other products.
- electrical appliances include dishwashers, dish dryers, refrigerators, washing machines, pots, TVs, personal computers, radio cassettes, cameras, video cameras, water purifiers, rice cookers, vegetable cutters, registers, and futons. There are dryer, FAX, ventilation fan, air conditioner, etc.
- Kitchen products include tableware, chopping board, push-cut, tray, chopsticks, tea dispenser, thermos, kitchen knife, stalk pattern, fry back, lunch box, rice paddle, bowl, drainer There are baskets, triangle corners, scrubbing, garbage baskets, and draining bags.
- Textile products include shower curtains, futon cotton, air conditioner filters, pantyhose, socks, towels, sheets, duvet covers, pillows, gloves, apron, curtains, diapers, bandages, masks, sportswear, etc.
- toiletries include toilet seats, bathtubs, tiles, pots, filth, toilet brushes, bath lids, pumice stones, soap containers, bath chairs, clothing baskets, showers, washstands, and paper products include wrapping paper,
- medicine wrapping paper There are medicine wrapping paper, medicine box, sketch book, medical chart, notebook, origami, and toys include dolls, stuffed animals, paper clay, blocks, puzzles and so on.
- leather products include shoes, bags, belts, watch bands, interior items, chairs, gloves, hanging leather, and stationery items include ballpoint pens, mechanical pens, pencils, erasers, crayons, paper, notebooks, flexible disks, There are ruler, post-it, stapler, etc.
- Other products include insoles, cosmetic containers, scrubbers, makeup puffs, hearing aids, musical instruments, cigarette filters, cleaning adhesive paper sheets, hanging leather grips, sponges, kitchen towels, cards, microphones, barber supplies, vending machines, razors, telephones, There are thermometers, stethoscopes, slippers, clothes cases, toothbrushes, sandbox sand, food packaging films, antibacterial sprays and paints.
- the median diameter is a value measured using a laser diffraction particle size distribution analyzer and analyzed on a volume basis.
- X-ray diffraction X-ray diffraction
- XRD diffraction was measured with CuK ⁇ rays at a measurement condition of 40 kV / 150 mA with a powder X-ray diffractometer (RINT2400V type, manufactured by Rigaku Corporation).
- RINT2400V type powder X-ray diffractometer
- the purity (mass%) of the brookite-type titanium oxide crystal was determined by ASTM File No. in the powder X-ray diffraction pattern.
- 29-1360 is used as a purity component derived from brookite-type titanium oxide crystal, while the X-ray diffraction derived from rutile, anatase, titanium oxyoxalate, etc.
- the peak X-ray diffraction intensity was used as an impurity component, and the X-ray diffraction intensity ratio was directly converted into a mass ratio, and the purity was calculated as the purity (mass%) of a brookite-type titanium oxide crystal with the entire crystal component as 100%.
- the sulfur atom content is determined from the content of titanium atoms and sulfur atoms measured with a fluorescent X-ray analyzer (ZSX-100e type, manufactured by Rigaku Corporation) in the entire titanium oxide (TiO 2 ). The content was calculated.
- the diffraction pattern was ASTM File No. Consistent with 48-1164.
- the X-ray diffraction intensity measured with a CuK ⁇ ray at 40 kV / 150 mA and a d value of 3.35 was 9,200 cps, and no diffraction peak derived from other than titanium oxyoxalate was observed. That is, crystalline titanium oxyoxalate having high purity was obtained.
- the volume-based median diameter was measured with a laser diffraction particle size distribution analyzer, the median diameter was 3.5 ⁇ m.
- Example 1 The crystalline titanium oxyoxalate obtained in Synthesis Example 1 was packed in a square mortar made of mullite, placed in a horizontal electric furnace, heated to 710 ° C. at 200 ° C./hour, heated at 710 ° C. for 10 hours, After cooling to 150 ° C. at 300 ° C./hour to 100 ° C./hour, it was crushed lightly in a mortar to obtain brookite type titanium oxide.
- Table 1 The results of measuring the median diameter, purity, particle shape, and sulfur content of the obtained product are shown in Table 1, the results of XRD diffraction measurement are shown in FIG. 1, and the electron micrograph is shown in FIG. In FIG.
- Example 2 The crystalline titanium oxyoxalate obtained in Synthesis Example 2 was packed in a mullite square mortar, placed in a gas furnace, heated to 600 ° C. at 200 ° C./hour, and then heated at 600 ° C. for 2 hours.
- Table 1 shows the results of measuring the median diameter, purity, particle shape, and sulfur content of the brookite-type titanium oxide obtained by lightly crushing in a mortar after cooling to 150 ° C. at 300 ° C./hour to 100 ° C./hour.
- the result of the XRD diffraction measurement is shown in FIG.
- Example 3 The crystalline titanium oxyoxalate obtained in Synthesis Example 3 is packed in a mullite square mortar coated with silicon carbide, placed in a horizontal electric furnace, heated to 750 ° C. at 200 ° C./hour, and then 750 ° C. For 2 hours.
- Table 1 shows the results of measuring the median diameter, purity, particle shape, and sulfur content of the brookite-type titanium oxide obtained by lightly crushing in a mortar after cooling to 150 ° C. at 300 ° C./hour to 100 ° C./hour.
- the result of the XRD diffraction measurement is shown in FIG.
- ⁇ Comparative Example 3> Commercially available amorphous titanium oxyoxalate was packed in a square mortar made of mullite, placed in a horizontal electric furnace, heated to 750 ° C. at 200 ° C./hour, and then heated at 750 ° C. for 2 hours. When the mixture was allowed to cool to 150 ° C. at 300 ° C./hour to 100 ° C./hour and then lightly crushed with a mortar, anatase-type titanium oxide containing rutile crystals was obtained. The results of measuring the median diameter, purity, particle shape, and sulfur content are shown in Table 1, and the results of XRD diffraction measurement are shown in FIG.
- TiOSO 4 ⁇ nH 2 O manufactured by Mitsuwa Chemicals Co., Ltd. titanium oxysulfate
- a square mortar made of mullite placed in a horizontal electric furnace, heated to 750 ° C. at 200 ° C./hour, then 750 Heated at 0 ° C. for 2 hours.
- anatase-type titanium oxide was obtained.
- the results of measuring the median diameter, purity, particle shape, and sulfur content are shown in Table 1, and the results of XRD diffraction measurement are shown in FIG.
- the manufacturing method of the brookite type titanium oxide powder of the present invention is a manufacturing method that is simple and industrially possible in terms of equipment and conditions and operation.
- 1 to 8 represents the X-ray diffraction intensity (unit: cps) in powder X-ray diffraction measurement. 1 to 8 represents the X-ray diffraction angle 2 ⁇ (unit: °).
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Abstract
Description
特許文献2には、アルカリ水溶液を加熱する従来公知の方法で得られるブルッカイト型酸化チタンは、粒子径が100μm以上と大きく、不均一であり、分散媒への分散性や透明性、被膜形成性、密着性、被膜硬度、耐摩耗性などが不十分であり、一方、特許文献2に開示された方法によれば平均粒子径1~600nmの微粒子酸化チタンが得られることの記載があったが、単相のブルッカイト型酸化チタンが得られたことの記載はなく、実施例に示されたブルッカイト型酸化チタンは含有量5~60%の混晶であった。
すなわち、単相であり、なおかつ平均粒子径が0.3μm~100μmの微粒子のブルッカイト型酸化チタンは知られておらず、そのような微粒子の製造方法も知られていなかったということができる。さらに、上記の二つの方法は、アルカリ液相中で加圧することにより沸点以上の温度で反応させる水熱反応が必須であり、危険な上に工業的に実施するにはコスト高であるため、安価に大量生産できるプロセスとは言えなかった。
更に、特許文献4の実施例には、平均粒子径100nmの単相微粒子ブルッカイト型酸化チタンが得られたことの記載があるが、他の粒径のものが得られたことの記載はなかった。また、製造方法としては「水熱処理」が必須であることが記載されており、また、多量のアンモニアを使用する必要があるなど、やはり工業的には決して容易ではない製造方法であった。
なお、本発明において、数値範囲を表す「下限~上限」の記載は、「下限以上、上限以下」を表し、「上限~下限」の記載は、「上限以下、下限以上」を表す。すなわち、上限及び下限を含む数値範囲を表す。また、本発明において、「質量%」と「重量%」とは同義であり、「質量部」と「重量部」とは同義である。
本発明のブルッカイト型結晶質酸化チタン粉末(以下、単に「ブルッカイト型酸化チタン粉末」または「ブルッカイト型酸化チタン」ともいう。)は、粉末X線回折図形がASTM File No.29-1360に示されるブルッカイト型酸化チタンの結晶構造を有する二酸化チタンである。結晶構造を示す代表的な具体的な格子面間隔d値は、3.51(100)、2.90(90)、3.47(80)、1.89(30)、1.66(30)、2.48(30)、1.69(20)、2.41(20)であり、()内の数値は最大ピークを示すd値3.51のピークのX線回折強度を100とした場合の相対比である。d値と回折角θの間には、2dSinθ=nλの関係があることはよく知られており、一般的に測定に用いられるCuKα線のλは1.5418オングストロームなのでn=1の回折を見た場合、d値3.51(100)に対応する、ブルッカイト型酸化チタン結晶の最強回折ピークは、回折角2θ=25.37°に現れる。また、ブルッカイト型酸化チタン結晶の次に強い回折ピークは、d値2.90(90)に対応する、回折角2θ=30.83°に現れるピークであり、アナターゼやルチルではd値2.90の付近には強い回折ピークは表れないので、CuKα線を用いて測定する場合、回折角2θ=30.83°のピーク強度によってブルッカイト型酸化チタン結晶の生成を、アナタースやルチルの影響なく確認することができる。常識的な測定条件である、40kV/150mAで、CuKα線を用いて測定した場合のX線回折強度cpsの絶対値で表現すると、回折角2θ=30.83において500cps以上が好ましく、より好ましくは1,000cps以上であり、さらに好ましくは2,000cps以上である。また、100,000cps以下であることが好ましい。本発明におけるブルッカイト型酸化チタン粉末の純度は粉末X線回折図形と不純物の含有量で確認することができ、粉末X線回折図形においてブルッカイト型酸化チタン粉末に帰属する以外のピークが、最大ピークであるd値3.51のX線回折強度の0%以上10%以下であることが好ましく、より好ましくは0%以上5%以下であり、さらに好ましくは0%、すなわち、これ以外のピークが観察されないものである。
また、本発明のブルッカイト型結晶質酸化チタン粉末の製造方法により、本発明のブルッカイト型結晶質酸化チタン粉末を容易に製造することができる。
本発明の製造方法で用いる結晶質オキシシュウ酸チタンに制限はないが、加熱後のブルッカイト型酸化チタンの品質に影響がでるため純度や粒度は制御されたものが好ましい。本発明に用いるオキシシュウ酸チタン結晶の粉末X線回折図形は、ASTM File No.48-1164に記されており、d値で3.35(100)、4.62(90)、3.22(78)、6.48(65)、4.24(62)、2.84(45)、1.88(44)、2.59(36)、4.18(26)、7.76(24)である。粉末X線回折図形において、オキシシュウ酸チタン粉末の特徴的な回折ピークであるd値3.35のX線回折ピークは、標準的な測定条件である、40kv/150mAで、CuKα線を用いて測定した場合は、回折角2θ=26.57°に現れる。X線回折強度cpsで表現すると、d値3.35のX線回折強度としては3,000cps以上が好ましく、そのような回折強度を示すオキシシュウ酸チタンを本発明では結晶質オキシシュウ酸チタンと呼び、本発明の製造方法における好ましい原料である。さらに好ましくは4,000cps以上のものである。また、100,000cps以下であることが好ましい。原料のオキシシュウ酸チタン結晶に酸化チタン結晶が混ざっていると、オキシシュウ酸チタン結晶の化学反応性が低下するので、酸化チタン結晶を示すX線強度は、20cps以下となることが好ましい。
結晶質オキシシュウ酸チタンの原料としては、入手が容易、かつ安価であり、結晶質オキシシュウ酸チタンを容易に生成できる観点から、オキシ硫酸チタニルを使用することが好ましい。
また、本発明の製造方法は、前記準備工程として、シュウ酸とオキシ硫酸チタニルとを少なくとも混合する工程を含むことが好ましく、シュウ酸とオキシ硫酸チタニルとを混合する工程、および、シュウ酸とオキシ硫酸チタニルとを少なくとも含む混合物を加熱熟成する工程を含むことがより好ましい。
原料の混合後に加熱熟成することでオキシシュウ酸チタンが容易に結晶化し、好ましい熟成の温度は、50℃~100℃である。また、熟成時間は、特に制限はないが、0.5~48時間であることが好ましく、1~20時間であることがより好ましい。得られたオキシシュウ酸チタン懸濁液は、セラミックフィルターや洗浄ろ過を繰り返す等の方法で脱イオン水を用いて洗浄し、ろ液の電気伝導度が0μS(ジーメンス)以上500μS以下になるまで水洗すると、不純物が除かれるので好ましい。
例えば、得られたブルッカイト型結晶質酸化チタン粉末を洗浄する工程、得られたブルッカイト型結晶質酸化チタン粉末又は洗浄したブルッカイト型結晶質酸化チタン粉末を乾燥する工程が挙げられる。
また、前記加熱工程や前記乾燥工程等の後、得られたブルッカイト型結晶質酸化チタンの粒子同士が一部くっつき二次粒子を形成している場合は、本発明の製造方法は、得られたブルッカイト型結晶質酸化チタンを解砕しブルッカイト型結晶質酸化チタン粉末を得る工程を含んでいてもよい。
本発明のブルッカイト型結晶質酸化チタン粉末は、光触媒能により消臭、防カビ、防藻および抗菌性を必要とされる種々の分野、即ち電化製品、台所製品、繊維製品、住宅建材製品、トイレタリー製品、紙製品、玩具、皮革製品、文具およびその他の製品などとして利用することができる。
さらに具体的用途を例示すると、電化製品としては食器洗浄機、食器乾燥機、冷蔵庫、洗濯機、ポット、テレビ、パソコン、ラジカセ、カメラ、ビデオカメラ、浄水器、炊飯器、野菜カッター、レジスター、布団乾燥器、FAX、換気扇、エアーコンデショナーなどがあり、台所製品としては、食器、まな板、押し切り、トレー、箸、給茶器、魔法瓶、包丁、おたまの柄、フライ返し、弁当箱、しゃもじ、ボール、水切り篭、三角コーナー、タワシいれ、ゴミ篭、水切り袋などがある。
その他の製品としてはインソール、化粧容器、タワシ、化粧用パフ、補聴器、楽器、タバコフィルター、掃除用粘着紙シート、吊革握り、スポンジ、キッチンタオル、カード、マイク、理容用品、自販機、カミソリ、電話機、体温計、聴診器、スリッパ、衣装ケース、歯ブラシ、砂場の砂、食品包装フィルム、抗菌スプレー、塗料などがある。
メジアン径は、レーザー回折式粒度分布計を用いて測定し、体積基準によって解析した値である。X線回折(XRD回折)は粉末X線回折装置(理学電機(株)製RINT2400V型)により測定条件40kV/150mAでCuKα線によって測定した。ブルッカイト型酸化チタン結晶の純度(質量%)は、粉末X線回折図形において、ASTM File No.29-1360に示されたブルッカイト型酸化チタン結晶粉末の示すX線回折強度を、ブルッカイト型酸化チタン結晶に由来する純度成分として、一方、ルチル、アナタース、オキシシュウ酸チタン等に由来するX線回折ピークのX線回折強度を不純物成分として、X線回折強度比をそのまま質量比に換算して、結晶成分全体を100%とするブルッカイト型酸化チタン結晶の純度(質量%)として算出した。硫黄原子含有量は、蛍光X線分析装置(理学電機(株)製ZSX-100e型)により測定されたチタン原子および硫黄原子の含有量から、酸化チタン(TiO2)全体の中での硫黄原子含有量を算出した。
容量1リットルのガラスフラスコに脱イオン水250mLとシュウ酸2水和物0.25モルを加え、30℃で溶解した。脱イオン水250mLにオキシ硫酸チタニル0.5モルを加え溶解した30℃の水溶液を20分かけて一定速度で滴下した。滴下終了後、1,000rpm、95℃で6時間撹拌した。その後、得られた沈殿物を脱イオン水でよく洗浄し、120℃で4時間乾燥後、解砕することでオキシシュウ酸チタンを合成した。得られたオキシシュウ酸チタンのXRD回折測定を行ったところ、回折図形はASTM File No.48-1164と一致した。40kV/150mAで、CuKα線を用いて測定した、d値3.35のX線回折強度は、9,200cpsであり、オキシシュウ酸チタン以外に由来する回折ピークは認められなかった。すなわち、純度の高い結晶質オキシシュウ酸チタンが得られた。次に、レーザー回折式粒度分布計で体積基準のメジアン径を測定したところ、メジアン径は3.5μmであった。
脱イオン水20Lにオキシ硫酸チタニル50モルを加え、50℃で溶解した。脱イオン水25Lにシュウ酸2水和物25モルを加え溶解した50℃の水溶液を10分で滴下した。滴下終了後、95℃に30分で昇温し、さらに8時間、500rpmで攪拌した。その後、得られた沈殿物をよく洗浄し、120℃で4時間乾燥後、解砕することでオキシシュウ酸チタンを合成した。得られたのはメジアン径14.5μmの結晶質オキシシュウ酸チタンであった。
容量1リットルのガラスフラスコ中で、脱イオン水250mLにシュウ酸2水和物0.25モルを加え、30℃で溶解した。脱イオン水250mLにオキシ硫酸チタニル0.5モルを加え溶解した30℃の水溶液を20分で滴下した。滴下終了後、1,000rpm、95℃で6時間攪拌した。その後、得られた沈殿物をよく洗浄し、120℃で4時間乾燥後、解砕することで結晶質オキシシュウ酸チタンを合成した。得られたのはメジアン径1.6μmの結晶質オキシシュウ酸チタンであった。
合成例1で得られた結晶質オキシシュウ酸チタンをムライト製角型匣鉢に詰めて横型電気炉に入れ、200℃/時間で710℃まで昇温後、710℃で10時間加熱した後、300℃/時間~100℃/時間で150℃まで放冷後に、乳鉢で軽く解砕してブルッカイト型酸化チタンが得られた。得られたもののメジアン径、純度、粒子形状、硫黄含有量を測定した結果を表1に、XRD回折測定の結果を図1に示し、電子顕微鏡写真を図9に示した。図1においてd値3.51(100)に対応する、ブルッカイト型酸化チタン結晶の最強回折ピークが2θ=25.37°に表れ、d値2.90(90)に対応する、回折角2θ=30.83°も大きく現れていたので図中、○で示した。その他のピークも、ブルッカイト型酸化チタンの標準ピークとよく一致しており、ほぼ単相のブルッカイト型酸化チタンが得られたことが確かめられた。
合成例2で得られた結晶質オキシシュウ酸チタンをムライト製角型匣鉢に詰めてガス炉に入れ、200℃/時間で600℃まで昇温後、600℃で2時間加熱した。300℃/時間~100℃/時間で150℃まで放冷後に乳鉢で軽く解砕し、得られたブルッカイト型酸化チタンのメジアン径、純度、粒子形状、硫黄含有量を測定した結果を表1、XRD回折測定の結果を図2に示した。
合成例3で得られた結晶質オキシシュウ酸チタンを、シリコンカーバイドでコーティングしたムライト製角型匣鉢に詰めて、横型電気炉に入れ、200℃/時間で750℃まで昇温後、750℃で2時間加熱した。300℃/時間~100℃/時間で150℃まで放冷後に乳鉢で軽く解砕し、得られたブルッカイト型酸化チタンのメジアン径、純度、粒子形状、硫黄含有量を測定した結果を表1、XRD回折測定の結果を図3に示した。
合成例3で得られた結晶質オキシシュウ酸チタンをムライト製角型匣鉢に詰めて横型電気炉に入れ、530℃まで200℃/時間で昇温後、530℃で10時間加熱した300℃/時間~100℃/時間で150℃まで放冷後に乳鉢で軽く解砕したところ、結晶性の低い酸化チタンが得られた。メジアン径、純度、粒子形状、硫黄含有量を測定した結果を表1、XRD回折測定の結果を図4に示した。
合成例3で得られた結晶質オキシシュウ酸チタンをムライト製角型匣鉢に詰めて横型電気炉に入れ、830℃まで200℃/時間で昇温後、830℃で1時間加熱した。300℃/時間~100℃/時間で150℃まで放冷後に乳鉢で軽く解砕したところ、ルチル型結晶を多量に含むブルッカイト型酸化チタンが得られた。メジアン径、純度、粒子形状、硫黄含有量を測定した結果を表1、XRD回折測定の結果を図5に示した。
市販の非晶質オキシシュウ酸チタンをムライト製角型匣鉢に詰めて横型電気炉に入れ、200℃/時間で750℃まで昇温後、750℃で2時間加熱した。300℃/時間~100℃/時間で150℃まで放冷後に乳鉢で軽く解砕したところ、ルチル型結晶を含むアナターゼ型酸化チタンが得られた。メジアン径、純度、粒子形状、硫黄含有量を測定した結果を表1、XRD回折測定の結果を図6に示した。
市販のオキシシュウ酸チタンアンモニウム(三津和化学薬品(株)製(NH4)2[Ti(C2O4)2O]・nH2O)をムライト製角型匣鉢に詰めて横型電気炉に入れ、200℃/時間で750℃まで昇温後、750℃で2時間加熱した。300℃/時間~100℃/時間で150℃まで放冷後に乳鉢で軽く解砕したところ、ルチル型酸化チタンが得られた。メジアン径、純度、粒子形状、硫黄含有量を測定した結果を表1、XRD回折測定の結果を図7に示した。
市販のオキシ硫酸チタン(三津和化学薬品(株)製TiOSO4・nH2O)をムライト製角型匣鉢に詰めて横型電気炉に入れ、200℃/時間で750℃まで昇温後、750℃で2時間加熱した。300℃/時間~100℃/時間で150℃まで放冷後に乳鉢で軽く解砕したところ、アナタース型酸化チタンが得られた。メジアン径、純度、粒子形状、硫黄含有量を測定した結果を表1、XRD回折測定の結果を図8に示した。
図1~図8の横軸はX線の回折角度2θ(単位:°)を表す。
Claims (9)
- レーザー回折式粒度分布計による体積基準のメジアン径が、0.3μm以上40μm以下の範囲内であり、粉末X線回折法による、ブルッカイト型結晶を90質量%以上含む、ブルッカイト型結晶質酸化チタン粉末。
- 硫黄原子含有量が0.05~1.5質量%である、請求項1に記載のブルッカイト型結晶質酸化チタン粉末。
- 結晶質オキシシュウ酸チタン粉末を準備する準備工程、および、
結晶質オキシシュウ酸チタン粉末を550℃~820℃の温度で加熱する加熱工程、を含む、ブルッカイト型結晶質酸化チタン粉末の製造方法。 - 前記加熱工程における加熱温度が600℃~810℃である、請求項3に記載のブルッカイト型結晶質酸化チタン粉末の製造方法。
- 前記加熱工程における加熱温度までの昇温速度が、10℃/時間~300℃/時間の間である、請求項3又は4に記載のブルッカイト型結晶質酸化チタン粉末の製造方法。
- 得られたブルッカイト型結晶質酸化チタン粉末が、レーザー回折式粒度分布計による体積基準のメジアン径が、0.3μm以上40μm以下の範囲内であり、粉末X線回折法による、ブルッカイト型結晶を90質量%以上含む、請求項3~5のいずれか1項に記載のブルッカイト型結晶質酸化チタン粉末の製造方法。
- 得られたブルッカイト型結晶質酸化チタン粉末における硫黄原子含有量が0.05~1.5質量%である、請求項3~6のいずれか1項に記載のブルッカイト型結晶質酸化チタン粉末の製造方法。
- 前記準備工程として、シュウ酸とオキシ硫酸チタニルとを少なくとも混合する工程を含む、請求項3~7のいずれか1項に記載のブルッカイト型結晶質酸化チタン粉末の製造方法。
- 前記準備工程として、シュウ酸とオキシ硫酸チタニルとを混合する工程、および、シュウ酸とオキシ硫酸チタニルとを少なくとも含む混合物を加熱熟成する工程をこの順で含む、請求項3~8のいずれか1項に記載のブルッカイト型結晶質酸化チタン粉末の製造方法。
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US (1) | US20140356627A1 (ja) |
JP (1) | JP5862683B2 (ja) |
KR (1) | KR20140112050A (ja) |
CN (1) | CN104144879A (ja) |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103427076A (zh) * | 2013-07-12 | 2013-12-04 | 新疆大学 | 一种固相化学反应制备TiO2-B纳米材料的方法 |
JP7043671B1 (ja) * | 2021-09-22 | 2022-03-29 | Jx金属株式会社 | ブルッカイト型結晶質酸化チタン粉末及びブルッカイト型結晶質酸化チタン粉末の製造方法 |
Families Citing this family (1)
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CN116375451A (zh) * | 2023-02-03 | 2023-07-04 | 淮南东辰固废利用有限公司 | 一种煤矸石生产陶粒用原料加工工艺 |
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- 2012-11-29 WO PCT/JP2012/080943 patent/WO2013099514A1/ja active Application Filing
- 2012-11-29 KR KR1020147020830A patent/KR20140112050A/ko not_active Application Discontinuation
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JP7043671B1 (ja) * | 2021-09-22 | 2022-03-29 | Jx金属株式会社 | ブルッカイト型結晶質酸化チタン粉末及びブルッカイト型結晶質酸化チタン粉末の製造方法 |
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KR20140112050A (ko) | 2014-09-22 |
JPWO2013099514A1 (ja) | 2015-04-30 |
CN104144879A (zh) | 2014-11-12 |
JP5862683B2 (ja) | 2016-02-16 |
TW201335072A (zh) | 2013-09-01 |
US20140356627A1 (en) | 2014-12-04 |
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