WO1997024289A1 - Dioxyde de titane a teneur fortement reduite en eau volatile, son procede d'obtention et melange-mere le contenant - Google Patents
Dioxyde de titane a teneur fortement reduite en eau volatile, son procede d'obtention et melange-mere le contenant Download PDFInfo
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- WO1997024289A1 WO1997024289A1 PCT/JP1996/003844 JP9603844W WO9724289A1 WO 1997024289 A1 WO1997024289 A1 WO 1997024289A1 JP 9603844 W JP9603844 W JP 9603844W WO 9724289 A1 WO9724289 A1 WO 9724289A1
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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
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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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
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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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3653—Treatment with inorganic compounds
- C09C1/3661—Coating
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3684—Treatment with organo-silicon compounds
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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
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
- C01P2006/82—Compositional purity water content
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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
Definitions
- Titanium dioxide with low volatile water content its production method and masterbatch containing it
- the present invention relates to a titanium dioxide powder having a small amount of volatile water, and thus, there is no risk of quality deterioration due to generation of air bubbles when embed into a synthetic resin product or the like, and a process for producing the same. Further, the present invention relates to a masterbatch comprising the above-mentioned titanium dioxide powder in a thermoplastic resin.
- the masterbatch is used when coloring and molding a thermoplastic resin, and is suitably used for a resin molded product having excellent high-speed and high-temperature processability, uniform and excellent concealing properties, particularly for a melt-extruded laminate film. Background technology
- Titanium dioxide (Ti02 : hereinafter sometimes abbreviated as titanium oxide) is known as a white pigment or an ultraviolet shielding agent, and is widely used as a coloring agent for blastix products and as a shielding agent.
- Additives such as titanium dioxide and fillers are kneaded by heating and melting the plastics, but the kneading temperature of polyolefin-based plastics and the like conventionally used for plastic films and sheets is limited. It is about 200, which is lower than Engineering Plastics, but recently, in order to improve productivity, the processing temperature of mixing, kneading, molding, etc. was traded back and forth at 300. There is a tendency to shorten processing time. In addition, the demands on the accuracy of the finished shape of products are becoming stricter. For this reason, very strict physical properties are required for titanium dioxide fine powder mixed with blastix.
- a titanium dioxide powder that can be easily dispersed in plastics, has a high hiding power, is excellent in weather resistance and light resistance, and generates a small amount of gas during processing.
- the effect of gas generation is inconspicuous at a mixing temperature of around 200.
- the organic components of the treating agent used to modify the surface of titanium dioxide are decomposed, or the gas components are vaporized due to elimination of water of crystallization, causing bubbles, which often leads to poor quality. are doing.
- a coloring composition is used when coloring the thermoplastic resin using the above-mentioned titanium oxide.
- this coloring composition a powdery dry color obtained by mixing a pigment and a dispersing agent, Liquid color or paste color in which pigments are dispersed in a liquid dispersant, master patches in which pellets are flaked by dispersing pigments at high concentration in solid resin at room temperature, etc. are used. I have. Above all, master batches are often used because they are easy to handle and work environment preservation during use.
- titanium oxide has excellent whiteness, high concealment, and high coloring power. It is used in large quantities as a white pigment for fat coloring.However, titanium oxide is inherently hydrophilic, and therefore has weather resistance. ⁇ Surface treatment with inorganic or organic substances is performed to improve hydrophobicity and dispersibility.
- titanium oxides treated with a polyol-based or polysiloxane-based surface treatment agent there are titanium oxides treated with a polyol-based or polysiloxane-based surface treatment agent.
- Tianium oxide surface-treated with a polyol-based surface treatment agent has good dispersibility but a small effect of hydrophobization. Therefore, a large amount of water is adsorbed, and the master batch using the surface-treated titanium oxide and the thermoplastic resin also has a small hydrophobicity, and thus contains a large amount of water.
- Titanium oxide that has been surface-treated with a polysiloxane-based treatment agent has a good hydrophobic effect, but the titanium oxide surface and the treatment agent have a weak chemical bonding force.
- the surface treatment agent peels off due to kneading conditions and extrusion conditions when manufacturing a master batch using a resin, and the dispersion state of the titanium oxide in the master batch varies and the hydrophobicity decreases. Increases water content.
- the water generated from the masterbatch in the extruder causes the masterbatch and the thermoplastic resin to slip.
- the raw material could not be supplied smoothly due to poor dispersion or moisture returning to the raw material supply port side of the processing machine.
- the water content is extremely important in the field of melt-extruded laminates, which require high-temperature processing, such as 280 to 350, at which desorption of water of crystallization occurs, and as the water content increases,
- high-temperature processing such as 280 to 350
- the present invention solves the above-mentioned problems in the conventional titanium dioxide, and has high dispersibility and hydrophobicity, and has a small amount of volatile moisture generated during high-temperature processing when kneading into synthetic resin products or the like.
- the purpose of the present invention is to provide a powder and a method for producing the same, and to provide a master batch with less moisture generated during high-temperature processing.
- the present invention provides, as preferred embodiments, an anatase-type titanium dioxide having a small amount of volatile water and high color stability, a method for producing the same, and a masterbatch containing the anatase-type titanium dioxide. Disclosure of the invention
- the titanium dioxide of the present invention is (1) titanium dioxide having a volatile water content of 80 ppm or less at a heat treatment temperature of 200 to 350, and (2) preferably having a volatile water content of It is less than 65 O ppm.
- the titanium dioxide of the present invention comprises (3) a divalent or trivalent uncolored cation having a 6-coordinate ionic radius of 0.6 A or more and 0.9 A or less contained in the crystal.
- Anatase type titanium dioxide with improved color stability includes those whose volatile water content at a heat treatment temperature of 200 to 350 is less than 80 Op ppn.
- Aluminum ions and zinc ions are preferable as cations to be introduced into the crystal.
- the amount of aluminum to be introduced is preferably from 0.02 to 0.4 wt% of aluminum and from 0.05 to 1.0: 1.0% of zinc. It is. (5) When both are introduced, it is appropriate that the total amount is 0.02 to 1.01% and the aluminum content is 0.4% or less.
- the size of the particles is preferably such that the average particle size of the primary particles is in the range of 0.01 to 1.0 ⁇ .
- the titanium dioxide powder contains 0.01 to 0.5 wt% of calcium salt and / or 0.05 to 3.0 wt% of calcium oxide in terms of calcium oxide.
- the above-mentioned production method comprises: (8) a method of adding an aluminate of 0.3 wt% or less in terms of alumina together with a calcium salt and / or a silane coupling agent, and (9) a treatment with a calcium clay followed by a silane coupling agent. (10) treatment with a calcium salt, followed by treatment with an aluminate, followed by treatment with a silane coupling agent, (11) treatment with the addition of an aluminate Includes a method of adding and processing a silane coupling agent.
- titanium dioxide powder may be used as an aqueous slurry, and the above-mentioned surface treatment agent such as calcium chloride may be added thereto, or (13) titanium dioxide powder is made into a fluid state by air current.
- the above surface treatment agent such as a calcium salt may be added thereto.
- a triethanolamine of 0.05 to 3.0 wt% may be used instead of the silane coupling agent, and (17) a calcium salt may be used.
- a magnesium salt of 0.01 to 0.5irt in terms of magnesium oxide may be used.
- Magnesium sulfate, magnesium chloride, magnesium bromide, or magnesium iodide can be used as the magnesium slope.
- a silicate having a titration of 0.3% or less may be used.
- the production method includes (20) a method of drying or pulverizing at a temperature of 200 or more after the surface treatment, and (21) a method of pulverizing in the presence of an organic dispersant after drying.
- (22) silane coupling agent, titanium coupling agent, silicone oil, polyhydric alcohol, At least one of lazan or alkanolamine can be used.
- a master batch containing the above titanium dioxide in a thermoplastic resin Specifically, (23) a master characterized in that titanium dioxide having a volatile water content of not more than 80 ⁇ ⁇ at a heat treatment temperature of 200 to 350 is contained in the thermoplastic resin.
- One batch is provided.
- the masterbatch of the present invention comprises (24) a divalent or trivalent uncolored cation having an ionic radius of 0.6 A or more and 0.9 A or less in the crystal, and A masterbatch characterized in that an anatase-type titanium dioxide having a volatile water content of 800 ppB or less at a heat treatment temperature of 50 is contained in a thermoplastic resin.
- the master batch is (25) 0.0 2 ⁇ 0.
- Aluminum and zinc contained in the crystal the total amount of both being 0.
- the average particle size of the secondary particles Includes masterbatch containing titanium dioxide of 0.01 to 1.0 m.
- the masterbatch of the present invention includes those containing titanium dioxide obtained by the above production method. Specifically, it includes the following.
- Titanium dioxide powder is treated by adding 0.01 to 0.5 wt% of calcium salt and / or 0.05 to 3.0 irt% of a silane coupling agent in terms of calcium oxide.
- a master batch characterized in that titanium dioxide whose volatile water content is not more than 80 ⁇ »at a heat treatment temperature of 200 to 350 is contained in a mature plastic resin.
- a master patch containing titanium dioxide treated with a calcium salt and then treated with a silane coupling agent (31) A master patch containing titanium dioxide, which is treated by adding calcium salt, then by adding an aluminate, and then by adding a silane coupling agent. (3 2) Aluminum A masterbatch containing titanium dioxide treated with an acid salt and then treated with a silane bonding agent. (33) A master patch containing titanium dioxide powder as an aqueous slurry, to which a calcium salt and / or a silane coupling agent, or a titanium oxide powder and an aluminate are added to provide a surface treatment.
- a master patch containing titanium dioxide powder which is made to be in a fluid state by an air current and contains calcium dioxide and / or a silane-based printing agent, or titanium dioxide which has been surface-treated by adding these to an aluminate.
- methyltrimethoxysilane, ⁇ -glycidoxybromotrimethoxysilane, ⁇ -aminobuchi pilltriethoxysilane, burtriethoxysilane, phenyltrialkoxysilane, and dialkyldialkoxysilane Masterbatch containing titanium dioxide treated using (37) A masterbatch containing titanium dioxide treated with 0.05 to 3.0 wt% of triethanolamine in place of the silane coupling agent. (38) A masterbatch containing titanium dioxide treated with a magnesium salt of 0.1 to 0.5 wt% in terms of magnesium oxide instead of calcium clay.
- the titanium dioxide powder of the present invention has a volatile water content of at most 80 O ppm, preferably at most 65 O ppB, at a heat treatment temperature of from 200 to 350.
- the titanium dioxide powder of the present invention does not use a treating agent containing water or an organic component that decomposes or separates in 200 to 350, but rather uses a treating agent that binds to hydroxyl groups on the surface of titanium dioxide. It fixes the hydroxyl groups on the surface of the titanium dioxide powder and suppresses the generation of water vapor during heat treatment.
- the main volatile component of the titanium dioxide powder is a hydroxyl group on the surface, and in the present invention, by fixing this to the powder surface, the amount of gas generated during the heat treatment was significantly suppressed.
- the method for producing the titanium dioxide powder used for the surface treatment of the present invention is not limited, and may be titanium dioxide obtained by a sulfuric acid method or titanium dioxide obtained by a chlorine method.
- the crystal type is not limited, and may be rutile-type titanium dioxide or anatase-type titanium dioxide.
- the particle size of titanium dioxide is appropriately selected according to the application. Generally, titanium dioxide used for paints, plastics, inks, papers, and the like has an average particle size of preferably from 0.01 to 1.0 / 1, and more preferably from 0.5 to 0.5 ⁇ m.
- anatase-type titanium dioxide those having improved color stability by containing non-colored cations in the crystal can be used.
- titanium dioxide crystals generally have some structural defects, and if these structural defects increase, the chemical stability decreases and the color tends to discolor at high temperatures.
- Conventional anatase-type titanium dioxide has lower color stability than rutile-type, but by introducing cations into this crystal to compensate for structural defects, it has high whiteness and discolors even under high temperature treatment. It is possible to obtain an anatase type titanium dioxide which is difficult and is excellent in light resistance and weather resistance.
- titanium dioxide crystals are formed by hexacoordinated titanium ions (Ti 4 + ), the cations introduced into the crystals are divalent or trivalent, and the hexacoordinated titanium ions (Ti 4 + + ) And the ionic radius are required to be similar and non-colored.
- titanium dioxide has an ionic radius of about 0.6 A or more and about 0.9 A or less, which is close to that of a hexacoordinated titanium ion (Ti 4 + ), and is divalent or trivalent.
- the above ionic radius is a value based on the radii of O 2 and F of six coordinates being 1.26 A and 1.19 A, respectively.
- Zions suitable for this condition include Al 3 + , Zn z ⁇ Ga 3 + , and Mg 2 + . Among them, aluminum ion and zinc ion are preferred from the viewpoint of effect and economy.
- the appropriate amount of aluminum to be introduced is 0.02 to 0.4 irt% of aluminum, 0.05 to 0.5% of zinc, and 1.0 wt% of zinc. In the case of introducing a heat exchanger, it is appropriate that the total amount is 0.02 to 1.0% and the aluminum content is 0.4% or less.
- the size of the titanium dioxide particles is preferably such that the average particle size of the primary particles is in the range of 0.01 to 1.0 / im.
- Anatase-type titanium dioxide in which aluminum and / or zinc is doped in the crystal is obtained by adding an aluminum compound and / or a water-soluble zinc compound to water-containing titanium dioxide obtained by hydrolysis of titanium sulfate, and then bringing the aluminum oxide and water-soluble zinc oxide into water. It can be manufactured by firing at 0 0 ⁇ .
- the surface-treated titanium dioxide powder of the present invention is obtained by a wet process in which the raw material titanium dioxide powder is converted into an aqueous slurry, the following surface treatment agent is added thereto, and the mixture is dried after the reaction.
- it can be obtained by a dry manufacturing method in which the raw material titanium dioxide powder is made into a fluid state, and the following surface treatment agent is jetted and reacted.
- the surface treatment agent calcium clay and a silane coupling agent are used, and an aluminate may be used in combination.
- a magnesium salt can be used instead of the calcium salt, and triethanolamine or the like can be used instead of the silane coupling agent.
- a silicate may be used in place of the aluminate.
- the calcium salt a calcium salt which does not decompose at 200 to 350 and binds to the hydroxyl group on the surface of the titanium dioxide powder to be dehydrated is used. Specifically, chloridium, calcium bromide, calcium iodide, calcium nitrate, etc. are suitable.
- An appropriate amount of the calcium salt to be added is 0.01 to 0.5 wt% in terms of calcium oxide (CaO) based on the solid content of titanium dioxide. Addition amount of the above calcium salt Power SO. /.
- the surface treatment is insufficient, and if the added amount is more than 0.5 wt%, Ca ions are not adsorbed and the surface treatment effect is not exhibited, but aluminate, silicate, etc. When used in combination with other surface treatment agents, they may form complex salts and exhibit adverse effects.
- the surface treatment with the calcium clay the surface of the titanium dioxide is dehydrated, and the surface of the titanium dioxide is coated with a dehydrated product to which calcium is bound.
- a silane coupling agent may be used in place of the calcium salt.
- the silane coupling agent reacts with the hydroxyl group on the surface of the titanium oxide to fix the hydroxyl group, thereby making the titanium oxide hydrophobic and improving the dispersibility.
- the surface treatment with a silane coupling agent in the case of a wet process, turns the raw material titanium dioxide powder into an aqueous slurry, adds a silane coupling agent to the slurry, stirs it uniformly, and then stands still for about 30 minutes. It is done by aging and drying. In the dry manufacturing method, a silane coupling agent is sprayed on a flowing titanium dioxide powder, allowed to stand, and then dried.
- silane coupling agent a silane coupling agent that is hardly decomposed at 200 to 350 ⁇ is used.
- silane coupling agent a silane coupling agent that is hardly decomposed at 200 to 350 ⁇ .
- those having structures represented by the following general formulas (1) to (), such as methyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, y-aminopropyltriethoxysilane examples include phenylalkoxysilanes such as roxyprovyl trimethoxysilane, vinyltriethoxysilane, phenylethanol alkoxysilane and diphenyldialkoxysilane, and dialkyldialkoxysilanes such as dimethyldimethoxysilane and dimethylethoxysilane.
- organic functional groups represented by the following general formulas (1) to () those having a methyl group or an amino group are preferred, and among them, dialkyldialkoxysi
- R divalent aliphatic pel, divalent aromatic chain
- the amount of silane coupling agent added is preferably 0.05 to 3.0% based on the solid content of titanium dioxide. It is preferably from 0.05 to: I. Oirt%, more preferably from 0.1 to 0.5 wt%, most preferably from 0:! To 0.3 wt%. If the addition amount is less than 0.05%, the bond with the hydroxyl group becomes insufficient, while if it is more than 3.0%, the silane coupling agent is condensed, and the surface treatment effect is saturated and the cost is reduced. It is not preferable because the height becomes higher.
- the surface-treated titanium dioxide is mixed with the resin, if the amount of the silane coupling agent exceeds 3.Oirt%, slip occurs at the time of resin extrusion and the ejection of the material becomes unstable. As a result, the colored composition cannot be manufactured stably. In particular, in the case of a film, the film thickness becomes non-uniform or the film breaks, making it impossible to form.
- the addition amount of the silane coupling agent is less than 0.1%, the effect of hydrophobizing the titanium oxide is small, and the amount of moisture absorbed over time after the production of the masterbatch increases, causing the same problem as before. .
- a surface treatment with an aluminate can further improve the surface properties.
- aluminate sodium aluminate, and as the aluminum salt, aluminum sulfate, aluminum nitrate, aluminum clay, and the like can be used.
- the addition of aluminate after the surface treatment with calcium clay forms a coating of hydrated alumina over the coating of the dehydrated product of calcium. Thereby, weather resistance and hiding property are improved.
- hydrated alumina contains structural water that evaporates in the range of 200 to 30 , the amount of hydrated alumina must be reduced to 0.3% or less in terms of alumina (A1203) to form a coating of hydrated alumina. It is suitable that the content is 0.1 to 0.2 irt%. If the amount used exceeds 0.3 irt%, the water content increases and troubles during processing are likely to occur.
- the surface treatment with the aluminate After performing the surface treatment with the aluminate, it is preferable to further perform the surface treatment using the silane coupling agent. Since the water-containing groups of the alumina coating are dehydrated by the surface treatment of the silane coupling agent, the amount of volatile water is further reduced.
- a silicate may be used in place of the aluminate clay. It is preferable to use aluminate from the viewpoint of excellent dispersibility.
- the amount of Kei salt is the same as aluminate, silicon dioxide (Si0 2) with respect to titanium dioxide in terms of solid content 0.3 wt% or less is suitable, and 0.1 to 0.2 stomach t% is preferable.
- Sodium silicate can be used as the silicate and silicon tetrachloride, ethyl silicate, etc. can be used as the silicon compound.
- a magnesium salt can be used in place of the calcium lump.
- the same effect as when calcium clay is used can be obtained by treatment with magnesium salt.
- magnesium salt a water-soluble magnesium salt such as magnesium sulfate, magnesium iodide, magnesium bromide, or magnesium iodide can be used.
- Magnesium mass may be used amount of almost the same as the calcium salt, 0. 0 1 ⁇ 0. 5wt% of magnesium oxide (M g 0) terms are appropriate for the titanium dioxide (solid).
- an alcohol such as a titanium coupling agent, silicone oil, polyhydric alcohol, alkyldisilazane or triethanolamine is used. Force nolamine may be used.
- addition 1 such as triethanolamine
- 0.05 to 3.0% of the solid content of titanium dioxide is appropriate, and preferably 0.05 to 3.0%.
- the titanium dioxide powder that has been subjected to the above surface treatment is filtered, dried and crushed.
- the drying temperature is preferably at least 200, and gas components that evaporate at a temperature range of less than 200 during this drying are removed. Further, after a surface treatment with a calcium salt is performed and dried, or when a pulverizing agent is added at the time of pulverization, the amount of volatile water can be further reduced. The amount added in this case may be the same as the amount added during the surface treatment of the water slurry.
- a titanium coupling agent silicone oil, polyhydric alcohol, or a Lucanolamine may be used.
- silicone oil silicone oil
- polyhydric alcohol polyhydric alcohol
- Lucanolamine Lucanolamine
- the amount of volatile components vaporized at a temperature of 200 to 35 is 80 Oppm or less, preferably 65 Oppm or less. Even when kneaded, the effects of air bubbles can be minimized.
- Table 1 shows the main surface treatment methods described above.
- the amounts of calcium salt, silane coupling agent, aluminate, silicate, triethanolamine, and magnesium salt added to titanium dioxide were all reduced to solid titanium dioxide.
- calcium clay is 0.01 to 0.5irt% in terms of calcium oxide
- silane coupling agent and triethanolamine is 0.05 to 3.0
- t% is 0.5% in terms of alumina. 3 * t% or less
- Magnesium salt in a range of 0.01 to 0.5 wt% in terms of magnesium oxide.
- the treatment method may be a wet method or a dry method. After the treatment, it is dried and pulverized to obtain the desired titanium dioxide powder. Adjust the pH as necessary.
- the titanium dioxide used in the masterbatch of the present invention has a volatile water content of not more than 80 O ppB, preferably not more than 65 ⁇ during heat treatment of 200 to 350, and is preferably calcium clay and silane coupling.
- Agents, magnesium salts used in place of these, magnesium salts used in place of calcium salts, triethanolamine used in place of silane coupling agents, or silicates used in place of aluminates Surface-treated, specifically, surface-treated by the above methods 1 to 24.
- the size of the titanium dioxide used in the master batch of the present invention is preferably from 0.01 to 1.0, more preferably from 0.1 to 0.5 ⁇ m.
- the crystal type may be either rutile type or anatase type, but anatase type is preferable in terms of whiteness.
- thermoplastic resin used in the present invention examples include general thermoplastic resins such as polyolefin resin, polyester resin, polystyrene resin, and nylon resin.
- polyolefin resins and polyester resins are particularly preferred for the extrusion extrusion laminate, and polyethylene-based resin is particularly preferred.
- polyester resin is particularly preferred for melt extrusion lamination on a metal substrate, and polyethylene terephthalate is particularly preferred.
- the masterbatch of the present invention comprises 100 to 400 parts by weight, preferably 100 to 300 parts by weight, most preferably 100 to 400 parts by weight of the above-mentioned titanium dioxide surface-treated with respect to 100 parts by weight of the thermoplastic resin. It is blended with 150 to 250 parts by weight.
- the masterbatch of the present invention has a volatile water content of 280 to 350 ⁇ below 1200 ppm or less, preferably 80 O ppB or less, and more preferably a volatile water content of 300 O ppB or less. It is below ppm.
- Volatile water content between 280 and 350
- the volatile water content is the water content generated at a predetermined temperature under a nitrogen atmosphere using a Karl-Fisher complete moisture meter, as in the case of the titanium dioxide powder.
- the master patch of the present invention is suitably used particularly for a melt extruded laminate film that requires high-temperature processing of 280 to 350 mm.
- the extruded laminating film is subjected to the high-temperature processing described above in order to require strong adhesion to the base material (paper, metal, etc.).
- the master batch of the present invention may contain, if necessary, other known additives such as other pigments and ultraviolet absorbers, as long as the effects are not impaired, other than the above components.
- Table 2 shows specific examples of the masterbatch according to the present invention.
- Example 1 the volatile water content was determined by dehydrating the titanium dioxide powder by heating at 200 for 1 hour and then heating at 350 to measure the amount of water vaporized. The heat dehydration was performed using a ring electric furnace, and the water content was measured using a Karl Fischer moisture meter (MKC-210, manufactured by Kyoto Electronics Industry Co., Ltd.).
- MKC-210 Karl Fischer moisture meter
- aqueous slurry containing anatase type titanium dioxide obtained by (Ti0 2: Concentration 500g / l) 2; the vector, the p H was added to sodium hydroxide aqueous solution 8 After adjusting to 5.5, sodium hexametaphosphate was added to obtain a dispersion slurry of titanium dioxide. After the slurry was pulverized with a sand mill, 0.1 wt% (2.63 g) of calcium dihydrate as CaO was added. After the slurry warmed to 60 Te Mitsurui was added 0. 2irt% aluminate sodium ⁇ beam as A 1 2 0 3 under a sufficient stirring condition. Then, the pH of the slurry was adjusted to 7.0 by dropwise addition of dilute sulfuric acid having a concentration of 10% over 30 minutes, and stirring was continued for 60 minutes in this state.
- Example 3 Removed filter cake is washed with water in Example 1, after a slurry of T i 0 2 concentration 4 0 O g eight by adding water before drying, as a silane coupling agent tau / - a Aminobu port built Rie Tokishishiran It was added 0. 5 wt% with respect to tau io 2. Except for this, the same treatment as in Example 1 was performed to obtain a titanium dioxide powder according to the method of the present invention. This titanium dioxide powder has a volatile water content of 480 ppm.
- Example 4 Example 4
- Example 3 sodium aluminate was not added, methyltrimethoxysilane was used as a silane coupling agent, and the mixture was pulverized by a hammer mill, and further pulverized by a steam micronizer using heated steam of 270. Except for this, the same treatment as in Example 3 was performed to obtain a titanium dioxide powder according to the method of the present invention. Amount of volatile water of the titanium dioxide powder was 4 3 0 pp m.
- Example 5 Amount of volatile water of the titanium dioxide powder was 4 3 0 pp m.
- Example 1 After pulverizing titanium dioxide powder was dried in a hammer mill, a Binirutorie Toki Shishiran was added 0.5% with respect to T i 0 2 as the silane force coupling agent placed in a Henschel mixer scratch. Except for this, the same treatment as in Example 1 was performed to obtain a titanium dioxide powder according to the method of the present invention. The volatile water content of this titanium dioxide powder was 48 O ppm.
- Example 1 the dried titanium dioxide powder was pulverized with a hammer mill, further pulverized with a steam micronizer using 27 o ⁇ ⁇ heated steam, and then put into a Henschel mixer, and dimethyl dimethyl was used as a silane coupling agent. Kishishiran was added 0.5 Les% relative T i 0 2. Otherwise, the same treatment as in Example 1 was performed to obtain a titanium dioxide powder according to the method of the present invention. The volatile water content of this titanium dioxide powder was 4.55 ppB.
- Example 7 A titanium dioxide powder according to the present invention was obtained in the same manner as in Example 6, except that calcium chloride was not used. The volatile water content of this titanium dioxide powder was 480 ppm.
- Example 8 A titanium dioxide powder according to the present invention was obtained in the same manner as in Example 6, except that calcium chloride was not used. The volatile water content of this titanium dioxide powder was 480 ppm.
- Example 1 the dried powder was pulverized by a hammer mill without adding sodium aluminate, and further pulverized by a steam mike using a heating steam of 27, and an organic solvent was added into the steam micronizer. Triethanolamine was added as a dispersant in an amount of 0.5 wt% with respect to titanium dioxide. Otherwise, the same treatment as in Example 1 was performed to obtain a titanium dioxide powder according to the present invention. The volatile water content of this titanium dioxide powder was 4.5 ppB.
- Example 10 the dried powder was pulverized with a hammer mill, and further pulverized with a steam micronizer using 27 heated steam. 0.5 wt% was added to titanium. Otherwise, the same treatment as in Example 1 was performed to obtain a titanium dioxide powder according to the present invention. The volatile water content of this titanium dioxide powder was 465 ppm.
- Example 10 The volatile water content of this titanium dioxide powder was 465 ppm.
- Example 1 In the same manner as in Example 1, except that sodium silicate (water glass No. 3) was added in an amount of 0.2% as the Si 2 in place of sodium aluminate, the same treatment was performed. A powder was obtained. The volatile water content of this titanium dioxide powder was 640 ppm.
- sodium silicate water glass No. 3
- Example 3 without adding calcium chloride, and 0.2 * by t% added pressure, also a silane coupling agent silicate sodium in place of the aluminate sodium U beam (water glass No. 3> As S i O z As ⁇ -aminobutyral piltriethoxy
- a silane coupling agent silicate sodium in place of the aluminate sodium U beam
- water glass No. 3> As S i O z As ⁇ -aminobutyral piltriethoxy A titanium dioxide powder according to the present invention was obtained in the same manner except that 0.5 * t% of methyltrimethysilane was added instead of silane.
- the volatile water content of this titanium dioxide powder was 68 Oppa.
- Example 1 2
- Example 3 "—aminopropyltriethoxysilane was replaced by 0.5 * t% of methyltrimethoxysilane as a silane coupling agent, and sodium silicate (water glass 3) was used instead of sodium aluminate. 0 No.) as S I_ ⁇ 2. except for using 2 wt% by the same treatment to obtain a titanium dioxide powder according to the invention. volatile water amount of the titanium dioxide powder is met 6 7 O ppm Example 13
- Example 3 0.5 wt% of triethanolamine was used instead of ⁇ -aminobutyritol triethoxysilane as a silane coupling agent, and sodium silicate (water glass No. 3) was used instead of sodium aluminate. the by the S I_ ⁇ 2 and of 0. 2 adventure t ⁇ the same process except for using 1 ⁇ 2, to obtain a titanium dioxide powder according to the invention. The volatile water content of this titanium dioxide powder was 655.5 ppm.
- Example 14 0.5 wt% of triethanolamine was used instead of ⁇ -aminobutyritol triethoxysilane as a silane coupling agent, and sodium silicate (water glass No. 3) was used instead of sodium aluminate. the by the S I_ ⁇ 2 and of 0. 2 adventure t ⁇ the same process except for using 1 ⁇ 2, to obtain a titanium dioxide powder according to the invention. The volatile water content of this titanium dioxide powder was 655.5 ppm.
- Example 15 the same treatment was carried out except that the addition rate of loamed calcium was changed to 0.5 wt% instead of 0.1 wt% in terms of CaO, and no sodium aluminate was added. Thus, a titanium dioxide powder according to the present invention was obtained. The volatile water content of this titanium dioxide powder was 53 O ppm.
- Example 15 The volatile water content of this titanium dioxide powder was 53 O ppm.
- Example 16 The same procedure was followed as in Example 3, except that calcium chloride and sodium aluminate were not added, and instead of ⁇ -aminobutyraltriethoxysilane, 0.5% of methyltrimethoxysilane was added.
- the titanium dioxide powder according to the present invention was obtained, and the titanium dioxide powder had a volatile water content of 505 ppm.
- Example 3 the same treatment was carried out except that calcium clay and sodium aluminate were not added, and that 0.5 wt% of triethanolamine was added instead of "y-aminopropyltriethoxysilane".
- Example 17 A titanium dioxide powder according to the present invention was obtained, and the volatile water content of the titanium dioxide powder was 53 Oppn.
- a titanium dioxide powder according to the present invention was prepared in the same manner as in Example 1 except that magnesium sulfate was replaced by 0.5% in terms of MgO and calcium aluminate was not used, and sodium aluminate was not used. I got The volatile water content of this titanium dioxide powder was 73 O ppm.
- Example 18
- Example 1 0.15 "% (4.48 g) of magnesium sulfate was used in place of calcium chloride in terms of MgO. A titanium powder was obtained, and the volatile water content of the titanium dioxide powder was 64 O ppm.
- Example 4 magnesium sulfate was used instead of calcium chloride at 0.5 wt% in terms of MgO. Except for this, the same treatment was performed to obtain a titanium dioxide powder according to the present invention. Amount of volatile water of the titanium dioxide powder is 5 8 O PPB der ivy 0 Example 2 0
- Example 8 A titanium dioxide powder according to the present invention was obtained in the same manner as in Example 8, except that magnesium sulfate was used instead of calcium chloride at 0.5 wt% in terms of MgO. The volatile water content of this titanium dioxide powder was 575 ⁇ .
- Example 2
- a titanium dioxide powder according to the present invention was obtained in the same manner as in Example 6, except that magnesium sulfate was replaced by 0.5% in terms of MgO in place of calcium clay. Amount of volatile water of the titanium dioxide powder c embodiment was 6 8 ⁇ ⁇ Example 2 2
- a titanium dioxide powder according to the present invention was obtained in the same manner as in Example 10, except that magnesium sulfate was replaced by 0.5 irt% in terms of MgO instead of calcium chloride.
- the volatile water content of this titanium dioxide powder was 67 O ppm.
- a titanium dioxide powder according to the present invention was obtained in the same manner as in Example 21, except that sodium silicate (water glass No. 3) was used in an amount of 0.2% as Si 2 instead of sodium aluminate. Was.
- the volatile water content of this titanium dioxide powder was 655.5 ppm.
- the results of the above examples are shown in Table 3.
- the volatile water content of the untreated titanium dioxide powder was also shown as a comparative sample. As shown in Table 3, the comparative sample without the surface treatment had a volatile water content of 130 O ppm, whereas the sample with the surface treatment of the present invention had a volatile water content of 64 O ppm or less. It is Byeon.
- the amount of volatile water can be further reduced by using a treatment with a calcium salt and a treatment with a silane coupling agent in combination, and further reduced by pulverizing with heated steam containing a silane coupling agent. Table 3
- ⁇ hydrous titanium dioxide slurry one obtained by hydrolyzing a titanium sulfate, washed, and titanium dioxide ⁇ 3 3% aqueous suspension ⁇ , the suspension 1 0 0 0 g (Ti0 2 in terms 330g ), Aluminum sulfate and zinc sulfate together with 1.3 g of lithium carbonate and 0.7 g of ammonium phosphate were adjusted to the amounts shown in Table 4 as aluminum (A1) and zinc (Zn), respectively. Added. After drying this mixed slurry, the mixture was allowed to stand in a ripening furnace at 80 for 1 hour, and then calcined at 960 for 3 hours, pulverized to obtain a dioxide having an average primary particle diameter of 0.20 win. A titanium powder was obtained.
- Example 8 X-ray diffraction confirmed that the powder was anatase-type titanium dioxide.
- the following light stability, whiteness and thermal stability of these titanium dioxide powders were measured, and the results are shown in Table 4. Further, the same surface treatment as in Example 8 was performed on the titanium dioxide powder of this example. The results are summarized in Table 4. As shown in Table 4, the titanium dioxide of this example has excellent light stability and heat stability, and has high whiteness. The amount of volatile water is also extremely low.
- the polyethylene sheet containing the titanium dioxide was heated at 310 for 20 minutes using a small Matsufuru furnace.
- the sheet was measured using the above color difference meter.
- the color difference from the sheet before heating is calculated using the Hunter color difference formula specified in JIS-Z-8370. Getting Out,
- Low-density polyethylene (specific gravity: 0.917, MFR 7.0 g / 10 min) and titanium dioxide with the surface treatment shown in Table 5 are mixed in a prescribed mixing ratio, heated and mixed by a kneader, cooled, pulverized, and extruded. It was extruded by a machine to obtain a pellet-shaped master batch. Various evaluation tests were performed on this master batch. The evaluation test was performed according to the following method. The results are summarized in Table 5. The combination of low-density polyethylene and surface-treated titanium dioxide! In Example 31, polyethylene 30 wt% and titanium dioxide 70 wt% in Example 31, polyethylene and titanium dioxide 5 Owt% each in Example 32, and polyethylene 4 Oirt% and titanium dioxide 6 O wt%.
- the amount of generated moisture (unit: ppm) at each temperature was measured using a Karl Fischer complete set moisture meter (manufactured by Hiranuma Sangyo Co., Ltd.).
- the above master patch 67 wt%, low density polyethylene (specific gravity 0.918, MFR 4.0 g / 10min) 33 wt% was blended, and using a T-die film forming machine (manufactured by Toyo Seiki Co., Ltd.), forming temperature 2 T-die films having a film thickness of 30 ⁇ were prepared at 80, 300, and 350, respectively, and the film formability (appearance) was evaluated.
- the master batch was 57 wt% and the low-density polyethylene was 43 wt%
- Example 38 the master batch was 80 wt% and the low-density polyethylene was 20 wt%. .
- the film forming property was evaluated by visually observing the presence or absence of lathing and the like.
- the symbols ⁇ , ⁇ , ⁇ , and X represent the following evaluations, respectively.
- the masterbatch of this example has a volatile water content of 100 ppm or less at a heat treatment temperature of 280 to 350, and most of the masterbatch is 300 ppm. ⁇ 500 ppm level.
- the volatile moisture of the comparative example! Is 1 1 0 0 ⁇
- the comparative example is inferior in film forming property
- the transmittance at each wavelength was measured using a colorimeter (manufactured by Kuraray Co., Ltd.) for the T-die film (thickness: 30 ⁇ ) extruded at 300 in Examples 34 and 35.
- the results in Table 6 were obtained.
- the higher the transmittance the lower the concealing property.
- the transmittance was as low as 2.01 to 2.53, and it was confirmed that the concealing property was good.
- a titanium dioxide powder having a volatile water content of 80 Oppn or less at a heat treatment temperature of 200 to 350 * C.
- this titanium dioxide powder is added to plastics and kneaded at the above temperature, the amount of volatile water is extremely small, so that there is no risk of quality deterioration due to bubbles. Therefore, it is possible to obtain a high quality product having excellent weather resistance and light resistance and high dimensional accuracy.
- This titanium dioxide powder can be easily produced by the production method of the present invention.
- the use of the surface-treated titanium dioxide provides excellent beading properties, dispersibility, and high-temperature processability, and High quality masterbatch with volatile water content at processing temperature of less than 120 ppm, preferably less than 800 ppm Is obtained,
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Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP96943324A EP0870731A4 (en) | 1995-12-27 | 1996-12-27 | TITANIUM DIOXIDE WITH A HIGHLY REDUCED VOLATILE WATER CONTENT, PROCESS FOR OBTAINING SAME AND MOTHER-MIXTURE CONTAINING SAME |
AU12092/97A AU1209297A (en) | 1995-12-27 | 1996-12-27 | Titanium dioxide reduced in volatile water content, process for producing the same, and masterbatch containing the same |
JP52419597A JP3584293B2 (ja) | 1995-12-27 | 1996-12-27 | 揮発水分量の少ない二酸化チタンとその製法およびこれを含有するマスターバッチ |
US09/091,884 US6126915A (en) | 1995-12-27 | 1996-12-27 | Titanium dioxide reduced in volatile water content, process for producing the same, and masterbatch containing the same |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP35128495 | 1995-12-27 | ||
JP7/351284 | 1995-12-27 | ||
JP8/212296 | 1996-08-12 | ||
JP21229696 | 1996-08-12 |
Publications (1)
Publication Number | Publication Date |
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WO1997024289A1 true WO1997024289A1 (fr) | 1997-07-10 |
Family
ID=26519129
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1996/003844 WO1997024289A1 (fr) | 1995-12-27 | 1996-12-27 | Dioxyde de titane a teneur fortement reduite en eau volatile, son procede d'obtention et melange-mere le contenant |
Country Status (5)
Country | Link |
---|---|
US (1) | US6126915A (ja) |
EP (1) | EP0870731A4 (ja) |
JP (1) | JP3584293B2 (ja) |
AU (1) | AU1209297A (ja) |
WO (1) | WO1997024289A1 (ja) |
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EP0977089A1 (en) * | 1998-07-30 | 2000-02-02 | Mitsubishi Chemical Corporation | Electrophotographic photosensitive member and process for producing the same |
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JPWO2004052786A1 (ja) * | 2002-12-09 | 2006-04-13 | テイカ株式会社 | 有益な性質を有する酸化チタン粒子およびその製造方法 |
EP1580166A4 (en) * | 2002-12-09 | 2010-08-25 | Tayca Corp | TITANIUM OXIDE PARTICLES HAVING USEFUL PROPERTIES, AND PROCESS FOR MAKING SAME |
WO2004052786A1 (ja) * | 2002-12-09 | 2004-06-24 | Tayca Corporation | 有益な性質を有する酸化チタン粒子およびその製造方法 |
US7611782B2 (en) | 2003-08-26 | 2009-11-03 | Japan As Represented By The President Of National Cardiovascular Center | Titanium oxide complex and production method thereof, and medical material using the same |
JP2007055875A (ja) * | 2005-08-26 | 2007-03-08 | Tayca Corp | 酸化チタン水性スラリーの濾過速度を改善する方法およびこの方法から得られた酸化チタン粉体 |
WO2007052851A1 (ja) * | 2005-11-07 | 2007-05-10 | Nippon Paper-Pak Co., Ltd. | マスターバッチ、該マスターバッチを用いて形成されたポリオレフィン層を有する積層材料及び該積層材料を用いて成形された紙製液体用容器 |
JP5178201B2 (ja) * | 2005-11-07 | 2013-04-10 | 日本製紙株式会社 | 無臭性紙製液体容器用マスターバッチ、該無臭性紙製液体容器用マスターバッチを用いて形成されたポリオレフィン層を有する無臭性紙製液体容器用積層材料及び該積層材料を用いて成形された無臭性紙製液体用容器 |
JP2009179670A (ja) * | 2008-01-30 | 2009-08-13 | Toyo Ink Mfg Co Ltd | 熱可塑性樹脂組成物 |
WO2021200485A1 (ja) * | 2020-03-31 | 2021-10-07 | デンカ株式会社 | アルミナ粉末、フィラー組成物、樹脂組成物、封止材、及び指紋認証センサー |
JP2022155422A (ja) * | 2021-03-30 | 2022-10-13 | 垰田 宏子 | 光触媒スラリーと光触媒マスターバッチと光触媒成形品とそれらの製造方法。 |
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JP3584293B2 (ja) | 2004-11-04 |
US6126915A (en) | 2000-10-03 |
EP0870731A1 (en) | 1998-10-14 |
EP0870731A4 (en) | 1999-02-03 |
AU1209297A (en) | 1997-07-28 |
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