WO2013183241A1 - Al-Ca-BASED INORGANIC FIBERS SOLUBLE IN PHYSIOLOGICAL SALINE AND COMPOSITION THEREFOR - Google Patents

Al-Ca-BASED INORGANIC FIBERS SOLUBLE IN PHYSIOLOGICAL SALINE AND COMPOSITION THEREFOR Download PDF

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WO2013183241A1
WO2013183241A1 PCT/JP2013/003252 JP2013003252W WO2013183241A1 WO 2013183241 A1 WO2013183241 A1 WO 2013183241A1 JP 2013003252 W JP2013003252 W JP 2013003252W WO 2013183241 A1 WO2013183241 A1 WO 2013183241A1
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composition
fiber
inorganic fibers
weight
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Japanese (ja)
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耕治 岩田
英樹 北原
持田　貴仁
賢 米内山
洋一 石川
達郎 三木
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ニチアス株式会社
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    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
    • C04B35/62231—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on oxide ceramics
    • C04B35/62236—Fibres based on aluminium oxide
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C13/00—Fibre or filament compositions
    • C—CHEMISTRY; METALLURGY
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/44—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminates
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
    • C04B35/62231—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on oxide ceramics
    • C04B35/6224—Fibres based on silica
    • C—CHEMISTRY; METALLURGY
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
    • C04B35/62231—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on oxide ceramics
    • C04B35/6224—Fibres based on silica
    • C04B35/62245—Fibres based on silica rich in aluminium oxide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/653—Processes involving a melting step
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2213/00—Glass fibres or filaments
    • C03C2213/02—Biodegradable glass fibres
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3213—Strontium oxides or oxide-forming salts thereof
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3272—Iron oxides or oxide forming salts thereof, e.g. hematite, magnetite
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    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
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    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/72—Products characterised by the absence or the low content of specific components, e.g. alkali metal free alumina ceramics
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    • C04B2235/9669—Resistance against chemicals, e.g. against molten glass or molten salts

Definitions

  • the present invention relates to an Al—Ca inorganic fiber excellent in biosolubility and alumina reaction resistance and a composition for obtaining the inorganic fiber.
  • conventional inorganic fibers are secondary-processed into shaped products and irregular shaped materials, together with various binders and additives, and joint materials in furnaces such as heat treatment equipment, industrial kilns and incinerators, It is used as a joint material, a sealing material, a packing material, a heat insulating material, and the like for filling gaps such as refractory tiles, heat insulating bricks, iron skin, and mortar refractories. Therefore, it is often exposed to high temperatures during use, and is required to have heat resistance. Current biosoluble fibers have insufficient heat resistance at 1400 ° C., and fibers that do not shrink significantly even at such high temperatures are preferable.
  • alumina is often used as a member in the furnace, and there is a problem that the fibers contained in the secondary processed product react with the alumina and the secondary processed product or member adheres or melts. .
  • An object of the present invention is to provide an inorganic fiber that is highly soluble in physiological saline at pH 4.5 and has excellent alumina reaction resistance and a composition for obtaining the inorganic fiber.
  • the following inorganic fiber composition and inorganic fiber are provided.
  • a composition for inorganic fibers having the following composition. Al 2 O 3 65.2-77.2 wt% CaO 22.8-34.8 wt% SiO 2 0 to 2.6% by weight The sum of Al 2 O 3 and CaO is more than 93.0% by weight. 2.
  • 3. The composition for inorganic fibers according to 1 or 2, wherein the total of Al 2 O 3 and CaO is more than 98.0% by weight.
  • a method for producing an inorganic fiber, wherein the melted inorganic fiber composition is formed into a fiber.
  • 6.4 A shaped product or an amorphous product obtained using the inorganic fiber described in 6.4.
  • an inorganic fiber having high solubility in physiological saline having a pH of 4.5 and excellent alumina reaction resistance and a composition for obtaining the inorganic fiber.
  • composition for inorganic fibers of the present invention has the following composition.
  • the sum of Al 2 O 3 and CaO is more than 93.0% by weight.
  • the total of Al 2 O 3 and CaO may be 95.0 wt% or more, more than 98.0 wt%, 99.0 wt% or more, or 100 wt%.
  • the rest other than Al 2 O 3 and CaO is oxides or impurities of other elements.
  • the amount of Al 2 O 3 can be 66.0% by weight or more, 68.5% by weight or more, or 71.0% by weight or more. Further, the amount of Al 2 O 3 can be 76.0% by weight or less, 75.0% by weight or less, or 74.5% by weight or less.
  • the amount of CaO can be 23.0 wt% or more, or 25.0 wt% or more. Further, the amount of CaO can be 33.0% by weight or less, 31.5% by weight or less, 31.0% by weight or less, or 29.0% by weight or less.
  • SiO 2 is 2.0 wt% or less, 1.0 wt% or less, can be 0.2 wt% or less, or 0.1 wt% or less, may not include.
  • the composition of the present invention comprises a respective oxide selected from Sc, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y or mixtures thereof. May or may not be included.
  • the amount of these oxides is 7 wt% or less, 5 wt% or less, 3 wt% or less, 2 wt% or less, 1.0 wt% or less, 0.5 wt% or less, 0.2 wt% or less, or It is good also as 0.1 weight% or less.
  • Each of the alkali metal oxides may or may not be contained, and is 7 wt% or less, 5 wt% or less, 3 wt% or less, 2 wt%, respectively. % Or less, 1.0% by weight or less, 0.5% by weight or less, 0.2% by weight or less, or 0.1% by weight or less.
  • Each of TiO 2 , ZnO, B 2 O 3 , P 2 O 5 , MgO, SrO, BaO, Cr 2 O 3 , ZrO 2 , and Fe 2 O 3 may or may not be included, each having a weight of 7 % Or less, 5% or less, 3% or less, 2% or less, 1.0% or less, 0.5% or less, 0.2% or less, or 0.1% or less. .
  • the amount of each component of the above composition may be arbitrarily combined.
  • composition of the present invention usually does not contain the following substances, or even contains them at 1.0% or less, 0.5% or less, 0.2% or less or 0.1% or less, respectively.
  • Inorganic fibers can be obtained from the composition of the present invention.
  • Inorganic fibers can be produced by a known method such as a melting method or a sol-gel method, but the melting method is preferred because of its low cost.
  • the melting method a melt containing CaO and Al 2 O 3 is produced, and the melt is made into a fiber.
  • it can be manufactured by a spinning method in which a melted raw material is poured onto a wheel rotating at high speed, and a blow method in which the melted raw material is fiberized by applying compressed air.
  • the fiber may be coated with a known coating material or may not be coated.
  • the fiber of the present invention has the same composition as that of the raw material, and by having the above composition, it has excellent solubility in physiological saline at pH 4.5 and excellent alumina reaction resistance.
  • the solubility in physiological saline having a pH of 4.5 is preferably 1.0 mg / g or more, more preferably 3.5 mg / g or more, and further preferably 4.0 mg / g or more, according to the measurement method of the example.
  • the solubility of the fiber can also be measured by the following method.
  • the fiber is placed on a membrane filter, pH 4.5 physiological saline is dropped on the fiber by a micropump, and the filtrate that has passed through the fiber and filter is stored in a container.
  • the accumulated filtrate is taken out after 24 and 48 hours, and the eluted components are quantified with an ICP emission spectrometer, and the solubility and dissolution rate constant are calculated.
  • the measurement element can be two elements of Al and Ca which are main elements.
  • the fiber diameter may be measured and converted to a dissolution rate constant k (unit: ng / cm 2 ⁇ h), which is an elution amount per unit surface area / unit time.
  • Alumina reactivity is the measurement method of the example, preferably with marks but not attached, and more preferably without attaching and without marks.
  • the fibers of the present invention preferably have heat resistance at 800 ° C or higher, 1000 ° C or higher, 1100 ° C or higher, 1200 ° C or higher, 1300 ° C or higher, or 1400 ° C or higher.
  • the volume shrinkage (%) obtained by heating a cylindrical sample having a diameter of about 7 mm and a height of about 15 mm at a predetermined temperature of 800 to 1400 ° C. for 8 hours is 40% or less at 1400 ° C. for 8 hours. , Preferably 30% or less, more preferably 23% or less, and most preferably 15% or less. It is 40% or less, preferably 30% or less, more preferably 23% or less, and most preferably 15% or less at 1300 ° C. for 8 hours.
  • the heat shrinkage rate of the fiber can be measured before and after the blanket is manufactured from the fiber and fired at 1100 ° C. or higher or 1200 ° C. or higher for 24 hours.
  • the tensile strength can be measured with a universal testing machine.
  • Specific applications of the fibers of the present invention include heat treatment equipment, joint materials in furnaces such as industrial kilns and incinerators, joint materials for filling gaps such as refractory tiles, heat insulating bricks, iron skins, mortar refractories, sealing materials, Packing material, cushioning material, heat insulating material, fireproofing material, fireproofing material, heat insulating material, protective material, coating material, filter material, filter material, insulating material, jointing material, filler, repair material, heat resistant material, noncombustible material, soundproofing material , Sound-absorbing materials, friction materials (for example, brake pad additives), glass plate / steel sheet transport rolls, automobile catalyst carrier support materials, various fiber reinforced composite materials (for example, fiber reinforced cement, fiber reinforced plastic and other reinforcing fibers, heat resistance Materials, reinforcing fibers of refractory materials, reinforcing fibers such as adhesives and coating materials), and the like.
  • various fiber reinforced composite materials for example, fiber reinforced cement, fiber reinforced plastic and other rein
  • Biosolubility 1 g of a sample was placed in an Erlenmeyer flask (volume: 300 mL) containing 150 mL of pH 4.5 physiological saline. This flask was placed in an incubator at 37 ° C., and horizontal vibration at 120 revolutions per minute was continued for 2.5 hours. Thereafter, the amount (mg) of each element contained in the filtrate obtained by filtration was measured with an ICP emission spectrometer, and the total was taken as the elution amount (mg / sample 1 g).
  • Alumina reactivity A sample was molded to obtain a cylindrical sample having a diameter of about 7 mm and a thickness of about 5 mm. This cylindrical sample was placed on an alumina plate and heated at 1400 ° C. for 8 hours to observe the presence or absence of adhesion or melting. It was 4 when the cylindrical sample was melted, 3 when it was adhered, 2 when it was not adhered but remained, and 1 when it was not adhered and remained.
  • Comparative Examples 2 and 3 Inorganic fiber A (ceramic fiber (conventional heat-resistant inorganic fiber)) containing 47% by mass of SiO 2 and 53% by mass of Al 2 O 3 (Comparative Example 2), 73% by mass of SiO 2 and 25% by mass of CaO Inorganic fiber B (conventional biosoluble fiber) (comparative example 3) containing 0.4% by mass of MgO and 2 % by mass of Al 2 O 3 was evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • the inorganic fiber of the present invention can be used for various purposes as a heat insulating material or as a substitute for asbestos.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Inorganic Fibers (AREA)
  • Ceramic Products (AREA)

Abstract

A composition for inorganic fibers which has a makeup comprising 65.2-77.2 wt% Al2O3, 22.8-34.8 wt% CaO, and 0-2.6 wt% SiO2, the sum of the Al2O3 and the CaO exceeding 93.0 wt%; inorganic fibers obtained from the composition for inorganic fibers; a process for inorganic-fiber production which comprises forming a melt of the composition for inorganic fibers into fibers; and an object having a definite or indefinite shape and obtained using the inorganic fibers.

Description

生理食塩水に可溶なＡｌ－Ｃａ系無機繊維及びその組成物Al-Ca inorganic fiber soluble in physiological saline and composition thereof
　本発明は、生体溶解性とアルミナ耐反応性に優れるＡｌ－Ｃａ系無機繊維とその無機繊維を得るための組成物に関する。 The present invention relates to an Al—Ca inorganic fiber excellent in biosolubility and alumina reaction resistance and a composition for obtaining the inorganic fiber.
　アスベストは、軽量で扱いやすく且つ耐熱性に優れるため、例えば、耐熱性のシール材として使用されていた。しかしアスベストは人体に吸入されて肺に疾患を引き起こすため使用が禁止され、これに代わりにセラミック繊維等が使用されている。セラミック繊維等は、耐熱性がアスベストに匹敵する程高く、適切な取り扱いをすれば健康上の問題は無いと考えられているが、より安全性を求められる風潮がある。そこで、人体に吸入されても問題を起こさない又は起こしにくい生体溶解性無機繊維を目指して、様々な生体溶解性繊維が開発されている（例えば、特許文献１，２）。 Since asbestos is lightweight, easy to handle and excellent in heat resistance, for example, it has been used as a heat-resistant sealing material. However, asbestos is inhaled by the human body and causes illness in the lungs, so its use is prohibited. Instead, ceramic fibers and the like are used. Ceramic fibers and the like have high heat resistance comparable to that of asbestos, and it is considered that there is no health problem if they are handled appropriately. However, there are trends that require more safety. Therefore, various biosoluble fibers have been developed aiming at biosoluble inorganic fibers that do not cause problems or are unlikely to occur even when inhaled by the human body (for example, Patent Documents 1 and 2).
　従来市販されている生体溶解性繊維はｐＨ７．４の生理食塩水に対し高い溶解性を持つ物がほとんどであった。一方で繊維が肺に吸入されるとマクロファージに捕り込まれることが知られており、マクロファージ周囲のｐＨは４．５であることも知られている。従って、ｐＨ４．５の生理食塩水に対する溶解性の高い繊維も、肺内で溶解、分解されることが期待される。 Most of the biosoluble fibers commercially available have a high solubility in physiological saline having a pH of 7.4. On the other hand, it is known that when the fiber is inhaled into the lung, it is trapped by macrophages, and the pH around the macrophages is also known to be 4.5. Therefore, it is expected that fibers having high solubility in physiological saline having a pH of 4.5 are dissolved and decomposed in the lung.
　また、従来の無機繊維は、アスベストと同様に、様々なバインダーや添加物とともに、定形物、不定形物に二次加工されて、熱処理装置、工業窯炉や焼却炉等の炉における目地材、耐火タイル、断熱レンガ、鉄皮、モルタル耐火物等の隙間を埋める目地材、シール材、パッキング材、断熱材等として用いられている。従って、使用の際は高温に晒されることが多く、耐熱性を有することが求められている。現在の生体溶解性繊維は１４００℃での耐熱性が不十分であり、このような高温でも大きく収縮しない繊維が好ましい。 In addition, as with asbestos, conventional inorganic fibers are secondary-processed into shaped products and irregular shaped materials, together with various binders and additives, and joint materials in furnaces such as heat treatment equipment, industrial kilns and incinerators, It is used as a joint material, a sealing material, a packing material, a heat insulating material, and the like for filling gaps such as refractory tiles, heat insulating bricks, iron skin, and mortar refractories. Therefore, it is often exposed to high temperatures during use, and is required to have heat resistance. Current biosoluble fibers have insufficient heat resistance at 1400 ° C., and fibers that do not shrink significantly even at such high temperatures are preferable.
　さらに、炉内の部材にアルミナが使用されていることが多く、二次加工品に含まれる繊維が、このアルミナと反応し二次加工品や部材が付着したり溶融したりする問題もあった。 In addition, alumina is often used as a member in the furnace, and there is a problem that the fibers contained in the secondary processed product react with the alumina and the secondary processed product or member adheres or melts. .
特許公報第３７５３４１６号Japanese Patent Publication No. 3753416 特表２００５－５１４３１８Special table 2005-514318
　本発明の目的は、ｐＨ４．５の生理食塩水に対する溶解性が高くアルミナ耐反応性に優れる無機繊維とその無機繊維を得るための組成物を提供することである。 An object of the present invention is to provide an inorganic fiber that is highly soluble in physiological saline at pH 4.5 and has excellent alumina reaction resistance and a composition for obtaining the inorganic fiber.
　本発明によれば、以下の無機繊維用組成物及び無機繊維等が提供される。
１．以下の組成を有する無機繊維用組成物。
　Ａｌ２Ｏ３　　　　　　　　　　６５．２～７７．２重量％
　ＣａＯ　　　　　　　　　　　　２２．８～３４．８重量％
　ＳｉＯ２　　　　　　　　　　　０～２．６重量％
　Ａｌ２Ｏ３とＣａＯの合計は９３．０重量％超である。
２．Ａｌ２Ｏ３が６８．５～７５．０重量％であり、ＣａＯが２５．０～３１．５重量％である１記載の無機繊維用組成物。
３．Ａｌ２Ｏ３とＣａＯの合計が９８．０重量％超である１又は２記載の無機繊維用組成物。
４．１～３のいずれか記載の無機繊維用組成物から得られる無機繊維。
５．溶融した１～３のいずれか記載の無機繊維用組成物を繊維化する無機繊維の製造方法。
６．４記載の無機繊維を用いて得られる定形物又は不定形物。 According to the present invention, the following inorganic fiber composition and inorganic fiber are provided.
1. A composition for inorganic fibers having the following composition.
Al 2 O 3 65.2-77.2 wt%
CaO 22.8-34.8 wt%
SiO 2 0 to 2.6% by weight
The sum of Al 2 O 3 and CaO is more than 93.0% by weight.
2. 2. The composition for inorganic fibers according to 1, wherein Al 2 O 3 is 68.5 to 75.0% by weight and CaO is 25.0 to 31.5% by weight.
3. The composition for inorganic fibers according to 1 or 2, wherein the total of Al 2 O 3 and CaO is more than 98.0% by weight.
4.1 Inorganic fibers obtained from the inorganic fiber composition according to any one of 1 to 3.
5). A method for producing an inorganic fiber, wherein the melted inorganic fiber composition is formed into a fiber.
6.4 A shaped product or an amorphous product obtained using the inorganic fiber described in 6.4.
　本発明によれば、ｐＨ４．５の生理食塩水に対する溶解性が高くアルミナ耐反応性に優れる無機繊維とその無機繊維を得るための組成物を提供することができる。 According to the present invention, it is possible to provide an inorganic fiber having high solubility in physiological saline having a pH of 4.5 and excellent alumina reaction resistance and a composition for obtaining the inorganic fiber.
　本発明の無機繊維用組成物は以下の組成を有する。
　Ａｌ２Ｏ３　　　　　　　　　　６５．２～７７．２重量％
　ＣａＯ　　　　　　　　　　　　２２．８～３４．８重量％
　ＳｉＯ２　　　　　　　　　　　０～２．６重量％
　Ａｌ２Ｏ３及びＣａＯの合計は９３．０重量％超である。 The composition for inorganic fibers of the present invention has the following composition.
Al 2 O 3 65.2-77.2 wt%
CaO 22.8-34.8 wt%
SiO 2 0 to 2.6% by weight
The sum of Al 2 O 3 and CaO is more than 93.0% by weight.
　Ａｌ２Ｏ３及びＣａＯの合計を、９５．０重量％以上、９８．０重量％超、９９．０重量％以上又は１００重量％としてもよい。
　Ａｌ２Ｏ３、ＣａＯ以外の残りは他の元素の酸化物又は不純物等である。 The total of Al 2 O 3 and CaO may be 95.0 wt% or more, more than 98.0 wt%, 99.0 wt% or more, or 100 wt%.
The rest other than Al 2 O 3 and CaO is oxides or impurities of other elements.
　Ａｌ２Ｏ３の量を、６６．０重量％以上、６８．５重量％以上又は７１．０重量％以上とすることができる。また、Ａｌ２Ｏ３の量を７６．０重量％以下、７５．０重量％以下又は７４．５重量％以下とすることができる。 The amount of Al 2 O 3 can be 66.0% by weight or more, 68.5% by weight or more, or 71.0% by weight or more. Further, the amount of Al 2 O 3 can be 76.0% by weight or less, 75.0% by weight or less, or 74.5% by weight or less.
　ＣａＯの量を、２３．０重量％以上、又は２５．０重量％以上とすることができる。また、ＣａＯの量を、３３．０重量％以下、３１．５重量％以下３１．０重量％以下又は２９．０重量％以下とすることができる。 The amount of CaO can be 23.0 wt% or more, or 25.0 wt% or more. Further, the amount of CaO can be 33.0% by weight or less, 31.5% by weight or less, 31.0% by weight or less, or 29.0% by weight or less.
　ＳｉＯ２は、２．０重量％以下、１．０重量％以下、０．２重量％以下又は０．１重量％以下とすることができ、含まなくてもよい。 SiO 2 is 2.0 wt% or less, 1.0 wt% or less, can be 0.2 wt% or less, or 0.1 wt% or less, may not include.
　本発明の組成物は、Ｓｃ，Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｓｍ，Ｅｕ，Ｇｄ，Ｔｂ，Ｄｙ，Ｈｏ，Ｅｒ，Ｔｍ，Ｙｂ，Ｌｕ，Ｙ又はこれらの混合物から選択されるそれぞれの酸化物を含んでも含まなくてもよい。これらの酸化物の量を、それぞれ７重量％以下、５重量％以下、３重量％以下、２重量％以下、１．０重量％以下、０．５重量％以下、０．２重量％以下又は０．１重量％以下としてもよい。 The composition of the present invention comprises a respective oxide selected from Sc, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y or mixtures thereof. May or may not be included. The amount of these oxides is 7 wt% or less, 5 wt% or less, 3 wt% or less, 2 wt% or less, 1.0 wt% or less, 0.5 wt% or less, 0.2 wt% or less, or It is good also as 0.1 weight% or less.
　アルカリ金属酸化物（Ｋ２Ｏ、Ｎａ２Ｏ、Ｌｉ２Ｏ等）の各々は含まれても含まれなくてもよく、それぞれ７重量％以下、５重量％以下、３重量％以下、２重量％以下、１．０重量％以下、０．５重量％以下、０．２重量％以下又は０．１重量％以下とすることができる。 Each of the alkali metal oxides (K 2 O, Na 2 O, Li 2 O, etc.) may or may not be contained, and is 7 wt% or less, 5 wt% or less, 3 wt% or less, 2 wt%, respectively. % Or less, 1.0% by weight or less, 0.5% by weight or less, 0.2% by weight or less, or 0.1% by weight or less.
　ＴｉＯ２、ＺｎＯ、Ｂ２Ｏ３、Ｐ２Ｏ５、ＭｇＯ、ＳｒＯ、ＢａＯ、Ｃｒ２Ｏ３、ＺｒＯ２、Ｆｅ２Ｏ３の各々は含まれても含まれなくてもよく、それぞれ７重量％以下、５重量％以下、３重量％以下、２重量％以下、１．０重量％以下、０．５重量％以下、０．２重量％以下又は０．１重量％以下とすることができる。 Each of TiO 2 , ZnO, B 2 O 3 , P 2 O 5 , MgO, SrO, BaO, Cr 2 O 3 , ZrO 2 , and Fe 2 O 3 may or may not be included, each having a weight of 7 % Or less, 5% or less, 3% or less, 2% or less, 1.0% or less, 0.5% or less, 0.2% or less, or 0.1% or less. .
　上記の組成の各成分の量を任意に組み合わせてもよい。 The amount of each component of the above composition may be arbitrarily combined.
　本発明の組成物は通常以下の物質を含まない、又は含んでもそれぞれ１．０重量％以下、０．５重量％以下、０．２重量％以下又は０．１重量％以下である。
　酸化ゲルマニウム、酸化テルル、酸化バナジウム、酸化イオウ、リン化合物、スズ、コバルト、酸化マンガン、フッ化物、酸化銅。 The composition of the present invention usually does not contain the following substances, or even contains them at 1.0% or less, 0.5% or less, 0.2% or less or 0.1% or less, respectively.
Germanium oxide, tellurium oxide, vanadium oxide, sulfur oxide, phosphorus compound, tin, cobalt, manganese oxide, fluoride, copper oxide.
　本発明の組成物から無機繊維を得ることができる。
　無機繊維は溶融法、ゾルゲル法等公知の方法で製造できるが、低コストのため溶融法が好ましい。溶融法では、ＣａＯ、Ａｌ２Ｏ３を含む溶融物を作製し、この溶融物を繊維化して製造する。例えば、高速回転しているホイール上に熔解した原料を流し当てることで繊維化するスピニング法及び熔解した原料に圧縮空気を当てることで繊維化するブロー法等により製造できる。 Inorganic fibers can be obtained from the composition of the present invention.
Inorganic fibers can be produced by a known method such as a melting method or a sol-gel method, but the melting method is preferred because of its low cost. In the melting method, a melt containing CaO and Al 2 O 3 is produced, and the melt is made into a fiber. For example, it can be manufactured by a spinning method in which a melted raw material is poured onto a wheel rotating at high speed, and a blow method in which the melted raw material is fiberized by applying compressed air.
　繊維は公知の被覆材により被覆されていてもよいし被覆されていなくてもよい。 The fiber may be coated with a known coating material or may not be coated.
　本発明の繊維は原料の組成の組成と同じであり、上記の組成を有することにより、ｐＨ４．５の生理食塩水に対する溶解性に優れ、アルミナ耐反応性に優れる。 The fiber of the present invention has the same composition as that of the raw material, and by having the above composition, it has excellent solubility in physiological saline at pH 4.5 and excellent alumina reaction resistance.
　ｐＨ４．５の生理食塩水に対する溶解性は、実施例の測定方法で、好ましくは１．０ｍｇ／ｇ以上、より好ましくは３．５ｍｇ／ｇ以上、さらに好ましくは４．０ｍｇ／ｇ以上である。 The solubility in physiological saline having a pH of 4.5 is preferably 1.0 mg / g or more, more preferably 3.5 mg / g or more, and further preferably 4.0 mg / g or more, according to the measurement method of the example.
　繊維の溶解性は以下の方法でも測定できる。
　繊維を、メンブレンフィルター上に置き、繊維上にマイクロポンプによりｐＨ４．５の生理食塩水を滴下させ、繊維、フィルターを通った濾液を容器内に貯める。貯めた濾液を２４、４８時間経過後に取り出し、溶出成分をＩＣＰ発光分析装置により定量し、溶解度及び溶解速度定数を算出する。例えば、測定元素は主要元素であるＡｌ、Ｃａの２元素とすることができる。尚、繊維径を測定して単位表面積・単位時間当たりの溶出量である溶解速度定数ｋ（単位：ｎｇ／ｃｍ２・ｈ）に換算してもよい。 The solubility of the fiber can also be measured by the following method.
The fiber is placed on a membrane filter, pH 4.5 physiological saline is dropped on the fiber by a micropump, and the filtrate that has passed through the fiber and filter is stored in a container. The accumulated filtrate is taken out after 24 and 48 hours, and the eluted components are quantified with an ICP emission spectrometer, and the solubility and dissolution rate constant are calculated. For example, the measurement element can be two elements of Al and Ca which are main elements. The fiber diameter may be measured and converted to a dissolution rate constant k (unit: ng / cm 2 · h), which is an elution amount per unit surface area / unit time.
　アルミナ反応性は、実施例の測定方法で、好ましくは痕は付くが付着せず、さらに好ましくは付着しないで痕も無いことである。 Alumina reactivity is the measurement method of the example, preferably with marks but not attached, and more preferably without attaching and without marks.
　本発明の繊維は、好ましくは８００℃以上、１０００℃以上、１１００℃以上、１２００℃以上、１３００℃以上又は１４００℃以上で耐熱性を有する。具体的には、直径約７ｍｍ、高さ約１５ｍｍの円柱状サンプルを８００～１４００℃の所定温度で８時間加熱して求めた体積収縮率（％）が、１４００℃－８時間で４０％以下、好ましくは３０％以下、更に好ましくは２３％以下、最も好ましくは１５％以下である。１３００℃－８時間で４０％以下、好ましくは３０％以下、更に好ましくは２３％以下、最も好ましくは１５％以下である。１２００℃－８時間で４０％以下、好ましくは３０％以下、更に好ましくは２３％以下、最も好ましくは１５％以下である。１１００℃－８時間で４０％以下、好ましくは３０％以下、更に好ましくは２３％以下、最も好ましくは１５％以下である。１０００℃－８時間で４０％以下、好ましくは３０％以下、更に好ましくは２３％以下、最も好ましくは１５％以下である。８００℃－８時間で４０％以下、好ましくは３０％以下、更に好ましくは２３％以下、最も好ましくは１５％以下である。 The fibers of the present invention preferably have heat resistance at 800 ° C or higher, 1000 ° C or higher, 1100 ° C or higher, 1200 ° C or higher, 1300 ° C or higher, or 1400 ° C or higher. Specifically, the volume shrinkage (%) obtained by heating a cylindrical sample having a diameter of about 7 mm and a height of about 15 mm at a predetermined temperature of 800 to 1400 ° C. for 8 hours is 40% or less at 1400 ° C. for 8 hours. , Preferably 30% or less, more preferably 23% or less, and most preferably 15% or less. It is 40% or less, preferably 30% or less, more preferably 23% or less, and most preferably 15% or less at 1300 ° C. for 8 hours. It is 40% or less, preferably 30% or less, more preferably 23% or less, and most preferably 15% or less at 1200 ° C. for 8 hours. It is 40% or less, preferably 30% or less, more preferably 23% or less, and most preferably 15% or less at 1100 ° C. for 8 hours. It is 40% or less, preferably 30% or less, more preferably 23% or less, and most preferably 15% or less at 1000 ° C. for 8 hours. It is 40% or less, preferably 30% or less, more preferably 23% or less, most preferably 15% or less at 800 ° C. for 8 hours.
　繊維の加熱収縮率は、繊維からブランケットを製造して１１００℃以上又は１２００℃以上で２４時間焼成した前後で測定することができる。また、引張強度は万能試験機により測定できる。 The heat shrinkage rate of the fiber can be measured before and after the blanket is manufactured from the fiber and fired at 1100 ° C. or higher or 1200 ° C. or higher for 24 hours. The tensile strength can be measured with a universal testing machine.
　本発明の繊維から、バルク、ブランケット、ブロック、ロープ、ヤーン、紡織品、界面活性剤を塗布した繊維、ショット（未繊維化物）を低減または取り除いたショットレスバルクや、水等の溶媒を使用し製造するボード、モールド、ペーパー、フェルト、コロイダルシリカを含浸したウェットフェルト、等の定形品が得られる。また、それら定形品をコロイドなどで処理した定形品が得られる。また、水等の溶媒を使用し製造する不定形材料（マスチック、キャスター、コーティング材等）も得られる。
　また、上記定形品、不定形品と各種発熱体を組み合わせた構造体も得られる。 Manufactured from fibers of the present invention using bulk, blankets, blocks, ropes, yarns, textiles, fibers coated with surfactants, shotless bulks with reduced or removed shots (unfibrinated), and solvents such as water Such as board, mold, paper, felt, wet felt impregnated with colloidal silica, and the like. In addition, a regular product obtained by treating the regular product with a colloid or the like can be obtained. Moreover, the amorphous material (mastic, a caster, a coating material, etc.) manufactured using solvents, such as water, is also obtained.
In addition, a structure in which the above-mentioned regular product, irregular product and various heating elements are combined can be obtained.
　本発明の繊維の具体的な用途として、熱処理装置、工業窯炉や焼却炉等の炉における目地材、耐火タイル、断熱レンガ、鉄皮、モルタル耐火物等の隙間を埋める目地材、シール材、パッキング材、クッション材、断熱材、耐火材、防火材、保温材、保護材、被覆材、ろ過材、フィルター材、絶縁材、目地材、充填材、補修材、耐熱材、不燃材、防音材、吸音材、摩擦材（例えばブレーキパット用添加材）、ガラス板・鋼板搬送用ロール、自動車触媒担体保持材、各種繊維強化複合材料（例えば繊維強化セメント、繊維強化プラスチックなどの補強用繊維、耐熱材、耐火材の補強繊維、接着剤、コート材などの補強繊維）等が例示される。 Specific applications of the fibers of the present invention include heat treatment equipment, joint materials in furnaces such as industrial kilns and incinerators, joint materials for filling gaps such as refractory tiles, heat insulating bricks, iron skins, mortar refractories, sealing materials, Packing material, cushioning material, heat insulating material, fireproofing material, fireproofing material, heat insulating material, protective material, coating material, filter material, filter material, insulating material, jointing material, filler, repair material, heat resistant material, noncombustible material, soundproofing material , Sound-absorbing materials, friction materials (for example, brake pad additives), glass plate / steel sheet transport rolls, automobile catalyst carrier support materials, various fiber reinforced composite materials (for example, fiber reinforced cement, fiber reinforced plastic and other reinforcing fibers, heat resistance Materials, reinforcing fibers of refractory materials, reinforcing fibers such as adhesives and coating materials), and the like.
実施例１～３、比較例１
　表１に示す繊維組成について以下のように検討した。
　まず、表１に示す組成となるように原料を混合し、プレス加工して成形体を得た。この成形体を加熱溶融し、急冷して得られた物を粉砕しサンプルを得た。このサンプルを用いて以下の方法で評価した。その結果を表１に示す。 Examples 1 to 3, Comparative Example 1
The fiber composition shown in Table 1 was examined as follows.
First, the raw materials were mixed so as to have the composition shown in Table 1, and pressed to obtain a molded body. The molded product was melted by heating and rapidly cooled to obtain a sample. Using this sample, the following method was used for evaluation. The results are shown in Table 1.
（１）生体溶解性
　サンプル１ｇを、ｐＨ４．５の生理食塩水１５０ｍＬが入った三角フラスコ（容積３００ｍＬ）に入れた。このフラスコを、３７℃のインキュベーター内に設置して、毎分１２０回転の水平振動を２．５時間継続した。その後、ろ過により得られた濾液に含有されている各元素の量（ｍｇ）をＩＣＰ発光分析装置により測定し、その合計を溶出量とした（ｍｇ／サンプル１ｇ）。 (1) Biosolubility 1 g of a sample was placed in an Erlenmeyer flask (volume: 300 mL) containing 150 mL of pH 4.5 physiological saline. This flask was placed in an incubator at 37 ° C., and horizontal vibration at 120 revolutions per minute was continued for 2.5 hours. Thereafter, the amount (mg) of each element contained in the filtrate obtained by filtration was measured with an ICP emission spectrometer, and the total was taken as the elution amount (mg / sample 1 g).
（２）アルミナ反応性
　サンプルを成形して、直径約７ｍｍ、厚み約５ｍｍの円柱状サンプルを得た。この円柱状サンプルをアルミナ板に載せて、１４００℃８時間加熱して、付着や溶融の有無を観察した。円柱状サンプルが溶融したときは４、付着したときは３、付着しないが痕が残ったときは２、付着もせず痕も残らないときは１とした。 (2) Alumina reactivity A sample was molded to obtain a cylindrical sample having a diameter of about 7 mm and a thickness of about 5 mm. This cylindrical sample was placed on an alumina plate and heated at 1400 ° C. for 8 hours to observe the presence or absence of adhesion or melting. It was 4 when the cylindrical sample was melted, 3 when it was adhered, 2 when it was not adhered but remained, and 1 when it was not adhered and remained.
（３）耐熱性
　サンプルを成形して、直径約７ｍｍ、高さ約１５ｍｍの円柱状サンプルを得た。この円柱状サンプルを１４００℃８時間加熱して、体積収縮率を求めた。 (3) Heat resistance A sample was molded to obtain a cylindrical sample having a diameter of about 7 mm and a height of about 15 mm. This columnar sample was heated at 1400 ° C. for 8 hours to determine the volume shrinkage.
比較例２，３
　ＳｉＯ２を４７質量％、Ａｌ２Ｏ３を５３質量％含む無機繊維Ａ（セラミック繊維（従来の耐熱性無機繊維））（比較例２）と、ＳｉＯ２を７３質量％、ＣａＯを２５質量％、ＭｇＯを０．４質量％、Ａｌ２Ｏ３を２質量％含む無機繊維Ｂ（従来の生体溶解性繊維）（比較例３）について、実施例１と同様に評価した。結果を表１に示す。 Comparative Examples 2 and 3
Inorganic fiber A (ceramic fiber (conventional heat-resistant inorganic fiber)) containing 47% by mass of SiO 2 and 53% by mass of Al 2 O 3 (Comparative Example 2), 73% by mass of SiO 2 and 25% by mass of CaO Inorganic fiber B (conventional biosoluble fiber) (comparative example 3) containing 0.4% by mass of MgO and 2 % by mass of Al 2 O 3 was evaluated in the same manner as in Example 1. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　本発明の無機繊維は、断熱材、またアスベストの代替品として、様々な用途に用いることができる。 The inorganic fiber of the present invention can be used for various purposes as a heat insulating material or as a substitute for asbestos.
　上記に本発明の実施形態及び／又は実施例を幾つか詳細に説明したが、当業者は、本発明の新規な教示及び効果から実質的に離れることなく、これら例示である実施形態及び／又は実施例に多くの変更を加えることが容易である。従って、これらの多くの変更は本発明の範囲に含まれる。
　この明細書に記載の文献及び本願のパリ優先の基礎となる日本出願明細書の内容を全てここに援用する。 Although several embodiments and / or examples of the present invention have been described in detail above, those skilled in the art will appreciate that these exemplary embodiments and / or embodiments are substantially without departing from the novel teachings and advantages of the present invention. It is easy to make many changes to the embodiment. Accordingly, many of these modifications are within the scope of the present invention.
The contents of the documents described in this specification and the specification of the Japanese application that is the basis of Paris priority of the present application are all incorporated herein.

Claims (6)

  1. 　以下の組成を有する無機繊維用組成物。
    　Ａｌ２Ｏ３　　　　　　　　　　６５．２～７７．２重量％
    　ＣａＯ　　　　　　　　　　　　２２．８～３４．８重量％
    　ＳｉＯ２　　　　　　　　　　　０～２．６重量％
    　Ａｌ２Ｏ３とＣａＯの合計は９３．０重量％超である。     A composition for inorganic fibers having the following composition.
    Al 2 O 3 65.2-77.2 wt%
    CaO 22.8-34.8 wt%
    SiO 2 0 to 2.6% by weight
    The sum of Al 2 O 3 and CaO is more than 93.0% by weight.
  2. 　Ａｌ２Ｏ３が６８．５～７５．０重量％であり、ＣａＯが２５．０～３１．５重量％である請求項１記載の無機繊維用組成物。 The composition for inorganic fibers according to claim 1, wherein Al 2 O 3 is 68.5 to 75.0 wt% and CaO is 25.0 to 31.5 wt%.
  3. 　Ａｌ２Ｏ３とＣａＯの合計が９８．０重量％超である請求項１又は２記載の無機繊維用組成物。 The composition for inorganic fibers according to claim 1 or 2, wherein the total of Al 2 O 3 and CaO is more than 98.0% by weight.
  4. 　請求項１～３のいずれか記載の無機繊維用組成物から得られる無機繊維。 An inorganic fiber obtained from the inorganic fiber composition according to any one of claims 1 to 3.
  5. 　溶融した請求項１～３のいずれか記載の無機繊維用組成物を繊維化する無機繊維の製造方法。 A method for producing inorganic fibers, wherein the melted composition for inorganic fibers according to any one of claims 1 to 3 is made into a fiber.
  6. 　請求項４記載の無機繊維を用いて得られる定形物又は不定形物。 A shaped product or an amorphous product obtained using the inorganic fiber according to claim 4.
PCT/JP2013/003252 2012-06-07 2013-05-22 Al-Ca-BASED INORGANIC FIBERS SOLUBLE IN PHYSIOLOGICAL SALINE AND COMPOSITION THEREFOR WO2013183241A1 (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06272116A (en) * 1992-08-26 1994-09-27 Didier Werke Ag Inorganic fiber
JP2002068769A (en) * 2000-08-23 2002-03-08 Taiheiyo Cement Corp Method of producing inorganic particle
JP2007303011A (en) * 2006-05-10 2007-11-22 Denki Kagaku Kogyo Kk Inorganic fiber and monolithic refractory using the same
JP2009542927A (en) * 2006-06-30 2009-12-03 ユニフラックス Ｉ リミテッド ライアビリティ カンパニー Inorganic fiber
JP2011106050A (en) * 2009-11-17 2011-06-02 Nichias Corp Method for producing inorganic fiber
JP2012102450A (en) * 2010-10-14 2012-05-31 Nichias Corp Inorganic fiber molded article, method for producing the same, and heating equipment

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06272116A (en) * 1992-08-26 1994-09-27 Didier Werke Ag Inorganic fiber
JP2002068769A (en) * 2000-08-23 2002-03-08 Taiheiyo Cement Corp Method of producing inorganic particle
JP2007303011A (en) * 2006-05-10 2007-11-22 Denki Kagaku Kogyo Kk Inorganic fiber and monolithic refractory using the same
JP2009542927A (en) * 2006-06-30 2009-12-03 ユニフラックス Ｉ リミテッド ライアビリティ カンパニー Inorganic fiber
JP2011106050A (en) * 2009-11-17 2011-06-02 Nichias Corp Method for producing inorganic fiber
JP2012102450A (en) * 2010-10-14 2012-05-31 Nichias Corp Inorganic fiber molded article, method for producing the same, and heating equipment

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