JP2014058423A - Biosoluble inorganic fiber having heat resistance and composition thereof - Google Patents
Biosoluble inorganic fiber having heat resistance and composition thereof Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 50
- 239000012784 inorganic fiber Substances 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 22
- 238000000034 method Methods 0.000 abstract description 14
- 238000002844 melting Methods 0.000 abstract description 7
- 230000008018 melting Effects 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000003980 solgel method Methods 0.000 abstract description 2
- 239000012768 molten material Substances 0.000 abstract 2
- 238000007796 conventional method Methods 0.000 abstract 1
- 239000000835 fiber Substances 0.000 description 29
- 239000000047 product Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000002504 physiological saline solution Substances 0.000 description 6
- 239000010425 asbestos Substances 0.000 description 5
- 210000004072 lung Anatomy 0.000 description 5
- 229910052895 riebeckite Inorganic materials 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- -1 B 2 O 3 Chemical compound 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- IKWTVSLWAPBBKU-UHFFFAOYSA-N a1010_sial Chemical compound O=[As]O[As]=O IKWTVSLWAPBBKU-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910000413 arsenic oxide Inorganic materials 0.000 description 1
- 229960002594 arsenic trioxide Drugs 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 210000002540 macrophage Anatomy 0.000 description 1
- 239000013521 mastic Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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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
- C04B35/62236—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
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/125—Silica-free oxide glass compositions containing aluminium as glass former
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- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/38—Fibrous materials; Whiskers
- C04B14/46—Rock wool ; Ceramic or silicate fibres
- C04B14/4618—Oxides
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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
- C04B35/6225—Fibres based on zirconium oxide, e.g. zirconates such as PZT
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- 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
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- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
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- 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
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- Inorganic Fibers (AREA)
Abstract
Description
本発明は、耐熱性を有する生体溶解性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 a biosoluble inorganic fiber having heat 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いが、生体溶解性が十分でないためやはり人体に吸入されて肺に侵入することによる問題が指摘されている。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）。 Asbestos has been used as, for example, a heat-resistant sealing material because it is lightweight, easy to handle, and excellent in heat resistance. 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. However, since the biosolubility is not sufficient, problems due to being inhaled into the human body and entering the lungs have been pointed out. 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).
従来の生体溶解性繊維の研究では、ｐＨ７．４の生理食塩水に対し溶解性の高い繊維を求めていた。しかしながら、繊維が吸入されるのは肺であり、肺のマクロファージのｐＨは４．５である。従って、ｐＨ４．５の生理食塩水に対する溶解性の高い繊維が、より効果的に肺内で溶解、分解されることが期待される。 In the study of conventional biosoluble fibers, fibers that are highly soluble in physiological saline at pH 7.4 have been sought. However, the fiber is inhaled by the lungs and the pH of the lung macrophages is 4.5. Therefore, it is expected that fibers having high solubility in physiological saline having a pH of 4.5 are dissolved and decomposed more effectively 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好ましい。また、炉においては壁面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壁面が付着したり溶融しないことが好ましい。 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 preferably has heat resistance. Further, alumina is often used for the wall surface in the furnace, and it is preferable that the fibers contained in the secondary processed product react with the alumina and the secondary processed product and the wall surface do not adhere or melt.
本発明の目的は、耐熱性を有する生体溶解性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 a biosoluble inorganic fiber having heat 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．Ａｌ２Ｏ３、ＣａＯ及びＺｒＯ２を、主成分として含む無機繊維用組成物。
２．以下の組成を有する１記載の無機繊維用組成物。
Ａｌ２Ｏ３ ０．１〜６４．０重量％
ＣａＯ １．０〜６１．０重量％
ＺｒＯ２ ３．０〜６０．０重量％
３．以下の組成を有する１又は２記載の無機繊維用組成物。
Ａｌ２Ｏ３ ０．１〜５９．０重量％
ＣａＯ ６．０〜５６．０重量％
ＺｒＯ２ ５．０〜５４．０重量％
４．以下の組成を有する１〜３のいずれか記載の無機繊維用組成物。
Ａｌ２Ｏ３ ０．１〜５７．０重量％
ＣａＯ ８．０〜５４．０重量％
ＺｒＯ２ ７．０〜５２．０重量％
５．Ａｌ２Ｏ３、ＣａＯ及びＺｒＯ２の合計は９０．０重量％以上である１〜４のいずれか記載の無機繊維用組成物。
６．Ａｌ２Ｏ３、ＣａＯ及びＺｒＯ２の合計は９８．０重量％以上である１〜５のいずれか記載の無機繊維用組成物。
７．Ａｌ２Ｏ3量が３０重量％以上である１〜６のいずれか記載の無機繊維。
８．ＺｒＯ２量が２５重量％以下である１〜７のいずれか記載の無機繊維。
９．１〜８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。
１０．溶融した１〜８のいずれか記載の無機繊維用組成物を繊維化する９記載の無機繊維の製造方法。
１１．９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 containing Al 2 O 3 , CaO and ZrO 2 as main components.
2. 2. Composition for inorganic fiber of 1 which has the following compositions.
Al 2 O 3 0.1 to 64.0% by weight
CaO 1.0 to 61.0% by weight
ZrO 2 3.0 to 60.0% by weight
3. The composition for inorganic fibers according to 1 or 2 having the following composition.
Al 2 O 3 0.1-59.0 wt%
CaO 6.0 to 56.0% by weight
ZrO 2 5.0-54.0 wt%
4). The composition for inorganic fiber in any one of 1-3 which has the following compositions.
Al 2 O 3 0.1~57.0 wt%
CaO 8.0 to 54.0% by weight
ZrO 2 7.0 to 52.0% by weight
5. The composition for inorganic fibers according to any one of 1 to 4, wherein the total of Al 2 O 3 , CaO and ZrO 2 is 90.0% by weight or more.
6). The composition for inorganic fibers according to any one of 1 to 5, wherein the total of Al 2 O 3 , CaO and ZrO 2 is 98.0% by weight or more.
7). The inorganic fiber according to any one of 1 to 6, wherein the amount of Al 2 O 3 is 30% by weight or more.
8). The inorganic fiber according to any one of 1 to 7, wherein the amount of ZrO 2 is 25% by weight or less.
The inorganic fiber obtained from the composition for inorganic fibers in any one of 9.1-8.
10. The method for producing inorganic fiber according to 9, wherein the melted composition for inorganic fiber according to any one of 1 to 8 is fiberized.
A shaped product or an amorphous product obtained using the inorganic fiber according to 11.9.
本発明によれば、耐熱性を有する生体溶解性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 a biosoluble inorganic fiber having heat resistance and a composition for obtaining the inorganic fiber.
本発明の繊維用組成物はＡｌ２Ｏ３、ＣａＯ及びＺｒＯ２を、主成分として含む。
主成分とは、組成物が含む全ての成分のうち最も含有量（重量％）の高い３成分がＡｌ２Ｏ３、ＣａＯ及びＺｒＯ２であることを意味する。
The fiber composition of the present invention contains Al 2 O 3 , CaO and ZrO 2 as main components.
The main component means that the three components having the highest content (% by weight) among all the components contained in the composition are Al 2 O 3 , CaO and ZrO 2 .
本発明の繊維用組成物は、好ましくは以下の組成を有する。
Ａｌ２Ｏ３ ０．１〜６４．０重量％
ＣａＯ １．０〜６１．０重量％
ＺｒＯ２ ３．０〜６０．０重量％
The fiber composition of the present invention preferably has the following composition.
Al 2 O 3 0.1 to 64.0% by weight
CaO 1.0 to 61.0% by weight
ZrO 2 3.0 to 60.0% by weight
上記の組成をさらに以下の組成とすることができる。
Ａｌ２Ｏ３ ０．１〜５９．０重量％
ＣａＯ ６．０〜５６．０重量％
ＺｒＯ２ ５．０〜５４．０重量％
The above composition can be further set as the following composition.
Al 2 O 3 0.1-59.0 wt%
CaO 6.0 to 56.0% by weight
ZrO 2 5.0-54.0 wt%
上記の組成をさらに以下の組成とすることができる。
Ａｌ２Ｏ３ ０．１〜５７．０重量％
ＣａＯ ８．０〜５４．０重量％
ＺｒＯ２ ７．０〜５２．０重量％
The above composition can be further set as the following composition.
Al 2 O 3 0.1~57.0 wt%
CaO 8.0 to 54.0% by weight
ZrO 2 7.0 to 52.0% by weight
Ａｌ２Ｏ３の含有量を３０重量％以上、又は３５重量％以上としてもよい。また、ＺｒＯ２の含有量を２５重量％以下、又は２３重量％以下としてもよい。 The content of Al 2 O 3 may be 30% by weight or more, or 35% by weight or more. Moreover, it is good also considering content of ZrO2 as 25 weight% or less or 23 weight% or less.
上記の組成において、生体溶解性の観点から、ＣａＯを１９．０重量％以上、２４．０重量％以上、３０．０重量％以上、又は４０．０重量％以上とすることができる。 In the above composition, from the viewpoint of biosolubility, CaO can be 19.0% by weight or more, 24.0% by weight or more, 30.0% by weight or more, or 40.0% by weight or more.
上記の組成の各成分の量を任意に組み合わせてもよい。
上記の各組成において、特定する成分の合計を、９０．０重量％以上、９５．０重量％以上、９７．０重量％以上、９８．０重量％以上、９９．０重量％以上又は１００．０重量％としてもよい。
特定する成分以外の残りは他の元素の酸化物又は不純物等である。
You may combine the quantity of each component of said composition arbitrarily.
In each of the above compositions, the total of the specified components is 90.0% by weight or more, 95.0% by weight or more, 97.0% by weight or more, 98.0% by weight or more, 99.0% by weight or more, or 100.% by weight. It may be 0% by weight.
The rest other than the specified components is oxides or impurities of other elements.
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５．０重量％以下、３．０重量％以下、２．０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 according to the 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 5.0 wt% or less, 3.0 wt% or less, 2.0 wt% or less, 1.0 wt% or less, 0.5 wt% or less, 0.2 wt% or less, respectively. 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、アルカリ金属酸化物はそれぞれ又は合計で５．０重量％以下、３．０重量％以下、２．０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 the alkali metal oxides are each or a total of 5.0% by weight or less. It can be 0 wt% or less, 2.0 wt% or less, 1.0 wt% or less, 0.5 wt% or less, 0.2 wt% or less, or 0.1 wt% or less.
ＴｉＯ２、ＺｎＯ、Ｂ２Ｏ３、Ｐ２Ｏ５、ＳｒＯ、ＢａＯ、Ｃｒ２Ｏ３、ＳｉＯ２、Ｆｅ２Ｏ３、ＭｇＯの各々は含まれても含まれなくてもよく、それぞれ５．０重量％以下、３．０重量％以下、２．０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 , SrO, BaO, Cr 2 O 3 , SiO 2 , Fe 2 O 3 , and MgO may or may not be included. 0 wt% or less, 3.0 wt% or less, 2.0 wt% or less, 1.0 wt% or less, 0.5 wt% or less, 0.2 wt% or less, or 0.1 wt% or less it can.
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０．２重量％以下又は０．１重量％以下である。
フッ素、硫酸カルシウム、酸化ヒ素、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、フッ素分子、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 if they contain 0.2% by weight or less or 0.1% by weight or less, respectively.
Fluorine, calcium sulfate, arsenic oxide, germanium oxide, tellurium oxide, vanadium oxide, sulfur oxide, fluorine molecule, 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。
本発明の繊維は溶融法、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、通常の方法により、原料の溶融物を作製し、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.
The fiber of the present invention 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 low cost. In the melting method, a raw material melt is produced by a normal method, 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.
本発明の繊維は公知の被覆材により被覆されていてもいなくてもよい。被覆により保存や使用時の溶解性を調整できる。 The fiber of the present invention may or may not be coated with a known coating material. The solubility during storage and use can be adjusted by coating.
本発明の繊維は、原料の組成物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（生体溶解性）を有する。
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１．５ｍｇ／ｇ以上、より好ましくは３．０ｍｇ／ｇ以上である。
The fiber of the present invention is the same as the composition of the raw material composition, and has solubility (biological solubility) in physiological saline having a pH of 4.5 by having the above composition.
The solubility in physiological saline having a pH of 4.5 is preferably 1.5 mg / g or more, more preferably 3.0 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.
本発明の繊維は、好ましくはアルミナ反応性が低い。アルミナ反応性は、実施例の測定方法で、好ましくは付着せず、より好ましくは痕は残るが付着しないこと、さらに好ましくは付着しないで痕も無いことである。 The fibers of the present invention preferably have low alumina reactivity. Alumina reactivity is preferably no adhesion, more preferably no trace but no adhesion, and even more preferably no adhesion and no trace in the measurement method of the Examples.
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、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℃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, 1400 ° C or higher. Specifically, the volumetric shrinkage (%) obtained by heating a cylindrical sample having a diameter of about 7 mm and a height of about 15 mm at 800-1400 ° C. for 8 hours is 40% or less at 1400 ° C.-8 hours, preferably 30% or less. It is 40% or less, preferably 30% or less, more preferably 23% or less, most preferably 15% or less at 1300 ° C. for 8 hours. It is 40% or less at 1200 ° 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 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, and 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℃，１２６０℃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 producing a blanket from the fiber and firing it at 1100 ° C. and 1260 ° C. for 24 hours. The tensile strength can be measured with a universal testing machine.
さらに、本発明の繊維は、必須成分の種類を少なくできるので、配合過程の工数が減り、コスト減となる。また微妙な配合量を調整する成分の種類が少ないことは製造の困難性を低減する。 Furthermore, since the fiber of this invention can reduce the kind of essential component, the man-hour of a compounding process reduces and it reduces cost. In addition, the fact that there are few kinds of components for adjusting delicate blending amounts reduces the difficulty of production.
本発明の繊維から、バルク、ブランケット、ブロックや、水等の溶媒を使用し製造するボード、モールド、ペーパー、フェルト等の定形品が得られる。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。 From the fiber of the present invention, bulk products, blankets, blocks, and shaped products such as boards, molds, papers and felts manufactured using a solvent such as water can be obtained. Moreover, the amorphous material (mastic, a caster, a coating material, etc.) manufactured using solvents, such as water, is also obtained.
実施例１〜６
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 1-6
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）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。
(2) 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.
（３）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。
(3) 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.
比較例１，２
ＳｉＯ２を４７質量％、Ａｌ２Ｏ３を５２質量％含むセラミック繊維（従来の耐熱性無機繊維）（比較例１）、及びＳｉＯ２を７０質量％、ＣａＯを２７質量％、ＭｇＯを０．５質量％、Ａｌ２Ｏ３を１質量％含む繊維（従来の生体溶解性繊維）（比較例２）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 1 and 2
Ceramic fiber (conventional heat-resistant inorganic fiber) containing 47% by mass of SiO 2 and 52% by mass of Al 2 O 3 (Comparative Example 1), 70% by mass of SiO 2 , 27% by mass of CaO, and 0.1% of MgO. A fiber (conventional biosoluble fiber) containing 5% by mass and 1% by mass of Al 2 O 3 (Comparative Example 2) was evaluated in the same manner as in Example 1. The results are shown in Table 1.
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 this invention can be used for various uses as a heat insulating material and a substitute for asbestos.
Claims (11)
Ａｌ２Ｏ３ ０．１〜６４．０重量％
ＣａＯ １．０〜６１．０重量％
ＺｒＯ２ ３．０〜６０．０重量％ The composition for inorganic fibers according to claim 1 having the following composition.
Al 2 O 3 0.1 to 64.0% by weight
CaO 1.0 to 61.0% by weight
ZrO 2 3.0 to 60.0% by weight
Ａｌ２Ｏ３ ０．１〜５９．０重量％
ＣａＯ ６．０〜５６．０重量％
ＺｒＯ２ ５．０〜５４．０重量％ The composition for inorganic fibers according to claim 1 or 2, having the following composition.
Al 2 O 3 0.1-59.0 wt%
CaO 6.0 to 56.0% by weight
ZrO 2 5.0-54.0 wt%
Ａｌ２Ｏ３ ０．１〜５７．０重量％
ＣａＯ ８．０〜５４．０重量％
ＺｒＯ２ ７．０〜５２．０重量％ The composition for inorganic fibers according to any one of claims 1 to 3, which has the following composition.
Al 2 O 3 0.1~57.0 wt%
CaO 8.0 to 54.0% by weight
ZrO 2 7.0 to 52.0% by weight
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS524520A (en) * | 1975-06-30 | 1977-01-13 | Fuji Fibre Glass Co Ltd | Composite of alkaliiproof glass |
| JPS5527866A (en) * | 1978-08-17 | 1980-02-28 | Nippon Sheet Glass Co Ltd | Glass composition for fiber |
| JPH0672029B2 (en) * | 1989-06-27 | 1994-09-14 | 株式会社島津製作所 | Fiber reinforced metal |
| JPH07211979A (en) * | 1994-01-19 | 1995-08-11 | Nippon Telegr & Teleph Corp <Ntt> | Fiber for optical amplifier |
| KR20080086542A (en) * | 2001-08-02 | 2008-09-25 | 쓰리엠 이노베이티브 프로퍼티즈 캄파니 | Method of making articles from glass and glass ceramic articles so produced |
-
2012
- 2012-09-18 JP JP2012204551A patent/JP2014058423A/en active Pending
-
2013
- 2013-09-02 WO PCT/JP2013/005160 patent/WO2014045527A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| WO2014045527A1 (en) | 2014-03-27 |
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