JP6386232B2 - Surface-modified inorganic fiber and method for producing the same - Google Patents
Surface-modified inorganic fiber and method for producing the same Download PDFInfo
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- JP6386232B2 JP6386232B2 JP2014023507A JP2014023507A JP6386232B2 JP 6386232 B2 JP6386232 B2 JP 6386232B2 JP 2014023507 A JP2014023507 A JP 2014023507A JP 2014023507 A JP2014023507 A JP 2014023507A JP 6386232 B2 JP6386232 B2 JP 6386232B2
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- 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
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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
- C03C13/00—Fibre or filament compositions
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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
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/42—Coatings containing inorganic materials
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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
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/42—Coatings containing inorganic materials
- C03C25/46—Metals
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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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
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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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/078—Glass compositions containing silica with 40% to 90% silica, by weight containing an oxide of a divalent metal, e.g. an oxide of zinc
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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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
- C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
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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
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
- C04B35/62844—Coating fibres
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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
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
- C04B35/62844—Coating fibres
- C04B35/62847—Coating fibres with oxide ceramics
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- 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
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
- C04B35/62844—Coating fibres
- C04B35/62847—Coating fibres with oxide ceramics
- C04B35/62849—Silica or silicates
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- 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
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
- C04B35/62844—Coating fibres
- C04B35/62847—Coating fibres with oxide ceramics
- C04B35/62852—Alumina or aluminates
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- 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
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
- C04B35/62886—Coating the powders or the macroscopic reinforcing agents by wet chemical techniques
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- 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
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/52—Constituents or additives characterised by their shapes
- C04B2235/5208—Fibers
- C04B2235/526—Fibers characterised by the length of the fibers
Description
本発明は、耐熱性に優れる表面改質無機繊維及びその製造方法に関する。 The present invention relates to a surface-modified inorganic fiber excellent in heat resistance and a method for producing the same.
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１，２，３）。 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, 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, 2, and 3).
一方、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。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。 On the other hand, inorganic fibers, like asbestos, are secondary-processed into regular and irregular shaped materials together with various binders and additives, heat treatment equipment, joint materials in furnaces such as industrial kilns and incinerators, refractory tiles. 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 heat insulating bricks, iron skins, and mortar refractories. When used, it is often exposed to high temperatures and is required to have heat resistance.
本発明の目的は、耐熱性の高い生体溶解性無機繊維を提供することである。 An object of the present invention is to provide biosoluble inorganic fibers having high heat resistance.
本発明者らが鋭意研究した結果、特定の改質剤で表面改質すると、加熱された際に繊維の表面結晶化が促進され、繊維の粘性流動、軟化、焼結等を抑制することで、耐熱性が改善されることを見出し本発明を完成された。
本発明によれば、以下の表面改質無機繊維等が提供される。
１．生体溶解性無機繊維の表面に、ケイ素及びその化合物、アルミニウム及びその化合物、カルシウム及びその化合物、マグネシウム及びその化合物、ジルコニウム及びその化合物、チタン及びその化合物、リン及びその化合物、鉄及びその化合物、シリカ及びその化合物、モリブデン及びその化合物、タングステン及びその化合物から選択される１以上の改質剤が、付着している表面改質無機繊維。
２．前記生体溶解性無機繊維が以下の組成を有する１記載の表面改質無機繊維。
ＳｉＯ２とＺｒＯ２とＡｌ２Ｏ３とＴｉＯ２との合計 ５０重量％〜８２重量％
アルカリ金属酸化物とアルカリ土類金属酸化物との合計 １８重量％〜５０重量％
３．前記生体溶解性無機繊維が、
シリカ、アルミナから選択される１以上と、
マグネシア、カルシア、ジルコニアから選択される１以上を、主成分として含む無機繊維である１記載の表面改質無機繊維。
４．前記生体溶解性無機繊維が、以下の組成を有する３記載の表面改質無機繊維。
シリカ、アルミナから選択される１以上 ０．３重量％〜９０重量％
マグネシア、カルシア、ジルコニアから選択される１以上 １０重量％〜６０重量％
５．前記生体溶解性無機繊維が、
シリカ、アルミナ、マグネシア、カルシアを、主成分として含む１又は２記載の表面改質無機繊維。
６．前記生体溶解性無機繊維が、
シリカ、マグネシア、ジルコニアを、主成分として含む１又は２記載の表面改質無機繊維。
７．前記生体溶解性無機繊維が、
シリカ、アルミナ、及びカルシア又はマグネシアを、主成分として含む１又は２記載の表面改質無機繊維。
８．前記生体溶解性無機繊維が、
シリカ、マグネシアを、主成分として含む１又は２記載の表面改質無機繊維。
９．前記生体溶解性無機繊維が、
シリカ、カルシアを、主成分として含む１又は２記載の表面改質無機繊維。
１０．前記生体溶解性無機繊維が、
シリカ、マグネシア、カルシアを、主成分として含む１又は２記載の表面改質無機繊維。
１１．前記生体溶解性無機繊維が、
ロックウール及びガラス繊維ではない１又は２記載の表面改質無機繊維。
１２．前記生体溶解性無機繊維の平均繊維長が、１０ｍｍ〜１００ｍｍである１〜１１のいずれか記載の表面改質無機繊維。
１３．前記改質剤が、シリカ、アルミナ、カルシア、マグネシア、ジルコニア、チタニア、酸化鉄、酸化リン、酸化モリブデン、酸化タングステン、モリブデン、及びタングステンから選択される１以上のみからなる１〜１２のいずれか記載の表面改質無機繊維。
１４．前記改質剤の量が、０．１質量％〜５０質量％である１〜１３のいずれか記載の表面改質無機繊維。
１５．前記改質剤が、アルミナ、マグネシア又はその両方を含む１〜１４のいずれか記載の表面改質無機繊維。
１６．前記改質剤が、モリブデン、モリブデン化合物又はその両方を含む１〜１４のいずれか記載の表面改質無機繊維。
１７．１〜１６のいずれか記載の表面改質無機繊維の製造方法であって、
生体溶解性無機繊維を、前記改質剤を含む溶液又は分散液に浸し、
前記生体溶解性無機繊維の表面に、前記改質剤を付着させる表面改質無機繊維の製造方法。
１８．１〜１６のいずれか記載の表面改質無機繊維の製造方法であって、
溶融した無機繊維原料に、空気を吹き付けて、生体溶解性無機繊維を製造する方法において、
前記改質剤を、共に吹きつけて、前記生体溶解性無機繊維の表面に、前記改質剤を付着させる表面改質無機繊維の製造方法。
１９．１〜１６のいずれか記載の表面改質無機繊維を用いて製造された二次製品又は複合材料。
As a result of intensive studies by the present inventors, when the surface is modified with a specific modifier, the surface crystallization of the fiber is promoted when heated, and the viscous flow, softening, and sintering of the fiber are suppressed. The present invention was completed by finding that the heat resistance was improved.
According to the present invention, the following surface-modified inorganic fibers and the like are provided.
1. On the surface of the biosoluble inorganic fiber, silicon and its compound, aluminum and its compound, calcium and its compound, magnesium and its compound, zirconium and its compound, titanium and its compound, phosphorus and its compound, iron and its compound, silica And a surface-modified inorganic fiber to which one or more modifiers selected from molybdenum and its compounds, tungsten and its compounds are attached.
2. 2. The surface-modified inorganic fiber according to 1, wherein the biosoluble inorganic fiber has the following composition.
The total of SiO 2 , ZrO 2 , Al 2 O 3 and TiO 2 50 wt% to 82 wt%
Total of alkali metal oxides and alkaline earth metal oxides 18% to 50% by weight
3. The biosoluble inorganic fiber is
One or more selected from silica and alumina;
2. The surface-modified inorganic fiber according to 1, which is an inorganic fiber containing one or more selected from magnesia, calcia, and zirconia as a main component.
4). 4. The surface-modified inorganic fiber according to 3, wherein the biosoluble inorganic fiber has the following composition.
1 or more selected from silica and alumina 0.3% by weight to 90% by weight
1 or more selected from magnesia, calcia, zirconia 10 wt% to 60 wt%
5. The biosoluble inorganic fiber is
3. The surface-modified inorganic fiber according to 1 or 2, comprising silica, alumina, magnesia, and calcia as main components.
6). The biosoluble inorganic fiber is
3. The surface-modified inorganic fiber according to 1 or 2, comprising silica, magnesia, zirconia as a main component.
7). The biosoluble inorganic fiber is
3. The surface-modified inorganic fiber according to 1 or 2 comprising silica, alumina, and calcia or magnesia as main components.
8). The biosoluble inorganic fiber is
3. The surface-modified inorganic fiber according to 1 or 2, comprising silica and magnesia as main components.
9. The biosoluble inorganic fiber is
3. The surface-modified inorganic fiber according to 1 or 2, comprising silica and calcia as main components.
10. The biosoluble inorganic fiber is
3. The surface-modified inorganic fiber according to 1 or 2 containing silica, magnesia, and calcia as main components.
11. The biosoluble inorganic fiber is
3. The surface-modified inorganic fiber according to 1 or 2, which is not rock wool or glass fiber.
12 The surface modified inorganic fiber according to any one of 1 to 11, wherein an average fiber length of the biosoluble inorganic fiber is 10 mm to 100 mm.
13. Any one of 1 to 12 wherein the modifier is composed of only one or more selected from silica, alumina, calcia, magnesia, zirconia, titania, iron oxide, phosphorus oxide, molybdenum oxide, tungsten oxide, molybdenum, and tungsten. Surface modified inorganic fiber.
14 The surface-modified inorganic fiber according to any one of 1 to 13, wherein the amount of the modifier is 0.1% by mass to 50% by mass.
15. The surface-modified inorganic fiber according to any one of 1 to 14, wherein the modifier includes alumina, magnesia, or both.
16. The surface-modified inorganic fiber according to any one of 1 to 14, wherein the modifier includes molybdenum, a molybdenum compound, or both.
17. A method for producing a surface-modified inorganic fiber according to any one of 1 to 16,
Immerse the biosoluble inorganic fiber in a solution or dispersion containing the modifier,
A method for producing a surface-modified inorganic fiber, wherein the modifying agent is attached to the surface of the biosoluble inorganic fiber.
18. A method for producing a surface-modified inorganic fiber according to any one of 1 to 16,
In the method for producing biosoluble inorganic fibers by blowing air to the molten inorganic fiber raw material,
The manufacturing method of the surface modification inorganic fiber which sprays together the said modifier and adheres the said modifier to the surface of the said biosoluble inorganic fiber.
The secondary product or composite material manufactured using the surface modified inorganic fiber in any one of 19.1-16.
本発明によれば、耐熱性の高い生体溶解性無機繊維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 high heat resistance.
本発明の表面改質無機繊維は、生体溶解性無機繊維の表面に、特定の改質剤が付着している。改質剤で、表面の一部又は全部が、被覆されている。改質剤で表面処理すると、耐熱性が改善され、例えば、加熱された際の繊維収縮を低下させたり、炉材との反応性を低下させたりする。 In the surface-modified inorganic fiber of the present invention, a specific modifier is attached to the surface of the biosoluble inorganic fiber. A part or all of the surface is coated with the modifier. When the surface treatment is performed with the modifier, the heat resistance is improved, and for example, the fiber shrinkage when heated or the reactivity with the furnace material is lowered.
本発明において生体溶解性とは、実施例に記載の測定方法でｐＨ７．４又はｐＨ４．５の生理食塩水に対する溶解速度定数が、１０ｎｇ／ｃｍ２・ｈ以上であることである。 In the present invention, biosolubility means that the dissolution rate constant for physiological saline of pH 7.4 or pH 4.5 is 10 ng / cm 2 · h or more by the measurement method described in the Examples.
本発明で用いる無機繊維は以下の組成を有することができる。
ＳｉＯ２とＺｒＯ２とＡｌ２Ｏ３とＴｉＯ２との合計 ５０重量％〜８２重量％
アルカリ金属酸化物とアルカリ土類金属酸化物との合計 １８重量％〜５０重量％
The inorganic fiber used in the present invention can have the following composition.
The total of SiO 2 , ZrO 2 , Al 2 O 3 and TiO 2 50 wt% to 82 wt%
Total of alkali metal oxides and alkaline earth metal oxides 18% to 50% by weight
また、本発明で用いる無機繊維は、シリカ、アルミナから選択される１以上と、マグネシア、カルシア、ジルコニアから選択される１以上を、主成分として含む繊維であってよい。 In addition, the inorganic fiber used in the present invention may be a fiber containing one or more selected from silica and alumina and one or more selected from magnesia, calcia, and zirconia as main components.
また、本発明で用いる無機繊維は、以下の組成を有することができる。
シリカ、アルミナから選択される１以上 ０．３重量％〜９０重量％
マグネシア、カルシア、ジルコニアから選択される１以上 １０重量％〜６０重量％
Moreover, the inorganic fiber used by this invention can have the following compositions.
1 or more selected from silica and alumina 0.3% by weight to 90% by weight
1 or more selected from magnesia, calcia, zirconia 10 wt% to 60 wt%
具体的には、以下の組成の無機繊維が例示できる。
（１）シリカ、アルミナ、マグネシア、カルシアを、主成分として含む無機繊維
（２）シリカ、アルミナ、カルシアを、主成分として含む無機繊維
（３）シリカ、アルミナ、マグネシアを、主成分として含む無機繊維
（４）シリカ、マグネシア、ジルコニアを、主成分として含む無機繊維
（５）シリカ、マグネシアを、主成分として含む無機繊維
（６）シリカ、カルシアを、主成分として含む無機繊維
（７）シリカ、マグネシア、カルシアを、主成分として含む無機繊維
（８）シリカ、マグネシア、ジルコニア、酸化モリブデンを、主成分として含む無機繊維
Specifically, inorganic fibers having the following composition can be exemplified.
(1) Inorganic fibers containing silica, alumina, magnesia and calcia as main components (2) Inorganic fibers containing silica, alumina and calcia as main components (3) Inorganic fibers containing silica, alumina and magnesia as main components (4) Inorganic fibers containing silica, magnesia and zirconia as main components (5) Inorganic fibers containing silica and magnesia as main components (6) Inorganic fibers containing silica and calcia as main components (7) Silica and magnesia Inorganic fiber containing calcia as main component (8) Inorganic fiber containing silica, magnesia, zirconia, molybdenum oxide as main component
主成分とは、無機繊維が含む全ての成分のうち含有量（重量％）の高い成分のことを意味する。
上記の繊維において、それぞれの主成分の合計が、繊維の総重量の８５重量％以上、９０重量％以上、９５重量％以上、９８重量％以上、９９重量％以上、又は９９．５重量％以上を占めてもよい。
例えば、「シリカ、アルミナ、マグネシア、カルシアを、主成分として含む無機繊維」では、シリカ、アルミナ、マグネシア、カルシアが、無機繊維が含む全ての成分のうち含有量（重量％）の高い１番目から４番目の成分である。そして、シリカ、アルミナ、マグネシア、カルシアの含有量の合計が、例えば、繊維の総重量の９５重量％以上を占めてもよい。
A main component means a component with high content (weight%) among all the components which an inorganic fiber contains.
In the above fibers, the total of the respective main components is 85% by weight or more, 90% by weight or more, 95% by weight or more, 98% by weight or more, 99% by weight or more, or 99.5% by weight or more of the total weight of the fiber. May occupy.
For example, in “inorganic fibers containing silica, alumina, magnesia, and calcia as main components”, silica, alumina, magnesia, and calcia are the first to have the highest content (% by weight) of all the components contained in inorganic fibers. The fourth component. And the sum total of content of a silica, an alumina, magnesia, and a calcia may occupy 95 weight% or more of the total weight of a fiber, for example.
上記無機繊維（１），（２）は、例えば、
シリカの含有量が０．３重量％〜７２重量％、
アルミナの含有量が１７重量％〜９０重量％、
マグネシアの含有量が０重量％〜３８重量％、
カルシアの含有量が０．２重量％〜６０重量％である。
The inorganic fibers (1) and (2) are, for example,
Silica content of 0.3 wt% to 72 wt%,
Alumina content of 17 wt% to 90 wt%,
The content of magnesia is 0% to 38% by weight,
The content of calcia is 0.2% to 60% by weight.
上記無機繊維（１）は、例えば、
シリカの含有量が０．４重量％〜６２重量％、
アルミナの含有量が２２重量％〜８０重量％、
マグネシアの含有量が１重量％〜２８重量％、
カルシアの含有量が０．３重量％〜５０重量％である。
The inorganic fiber (1) is, for example,
The silica content is 0.4 wt% to 62 wt%,
Alumina content of 22 wt% to 80 wt%,
The content of magnesia is 1% to 28% by weight,
The content of calcia is 0.3 wt% to 50 wt%.
上記無機繊維（１）は、例えば、
シリカの含有量が０．９重量％〜５２重量％、
アルミナの含有量が３２重量％〜７０重量％、
マグネシアの含有量が３重量％〜１８重量％、
カルシアの含有量が０．４重量％〜４０重量％である。
The inorganic fiber (1) is, for example,
Silica content is 0.9 wt% to 52 wt%,
The alumina content is 32 wt% to 70 wt%,
The content of magnesia is 3-18% by weight,
The content of calcia is 0.4 wt% to 40 wt%.
上記無機繊維（３）は、例えば、
シリカの含有量が１２重量％〜５１重量％、
アルミナの含有量が３４重量％〜７２重量％、
マグネシアの含有量が０．５重量％〜４２重量％である。
The inorganic fiber (3) is, for example,
A silica content of 12% to 51% by weight,
The alumina content is 34 wt% to 72 wt%,
The content of magnesia is 0.5% to 42% by weight.
上記無機繊維（３）は、例えば、
シリカの含有量が１７重量％〜４１重量％、
アルミナの含有量が３９重量％〜６２重量％、
マグネシアの含有量が２重量％〜３２重量％である。
The inorganic fiber (3) is, for example,
The silica content is 17 wt% to 41 wt%,
The alumina content is 39 wt% to 62 wt%,
The content of magnesia is 2% to 32% by weight.
上記無機繊維（３）は、例えば、
シリカの含有量が２７重量％〜３１重量％、
アルミナの含有量が４９重量％〜５２重量％、
マグネシアの含有量が１２重量％〜２２重量％である。
The inorganic fiber (3) is, for example,
The silica content is 27 wt% to 31 wt%,
The alumina content is 49 wt% to 52 wt%,
The content of magnesia is 12 to 22% by weight.
上記無機繊維（４）は、例えば、
シリカの含有量が３５重量％〜７５重量％、
マグネシアの含有量が１５重量％〜５５重量％、
ジルコニアの含有量が０．５重量％〜２７重量％である。
The inorganic fiber (4) is, for example,
A silica content of 35% to 75% by weight,
The content of magnesia is 15% to 55% by weight,
The content of zirconia is 0.5% by weight to 27% by weight.
上記無機繊維（４）は、例えば、
シリカの含有量が４５重量％〜６５重量％、
マグネシアの含有量が２５重量％〜４５重量％、
ジルコニアの含有量が１重量％〜１７重量％である。
The inorganic fiber (4) is, for example,
A silica content of 45 wt% to 65 wt%,
The content of magnesia is 25% to 45% by weight,
The content of zirconia is 1% by weight to 17% by weight.
上記無機繊維（５）は、例えば、
シリカの含有量が５０重量％〜９０重量％、
マグネシアの含有量が１０重量％〜５０重量％である。
The inorganic fiber (5) is, for example,
Silica content of 50 wt% to 90 wt%,
The content of magnesia is 10% to 50% by weight.
上記無機繊維（５）は、例えば、
シリカの含有量が６０重量％〜８０重量％、
マグネシアの含有量が２０重量％〜４０重量％である。
The inorganic fiber (5) is, for example,
Silica content of 60 wt% to 80 wt%,
The content of magnesia is 20% by weight to 40% by weight.
上記無機繊維（６）は、例えば、
シリカの含有量が２０重量％〜８５重量％、
カルシアの含有量が１５重量％〜８０重量％である。
The inorganic fiber (6) is, for example,
The silica content is 20 wt% to 85 wt%,
The content of calcia is 15% by weight to 80% by weight.
上記無機繊維（６）は、例えば、
シリカの含有量が５０重量％〜８５重量％、
カルシアの含有量が１５重量％〜５０重量％である。
The inorganic fiber (6) is, for example,
Silica content of 50 wt% to 85 wt%,
The content of calcia is 15% by weight to 50% by weight.
上記無機繊維（７）は、例えば、
シリカの含有量が２０重量％〜９０重量％、
マグネシアの含有量が５重量％〜４０重量％、
カルシアの含有量が５重量％〜４０重量％である。
The inorganic fiber (7) is, for example,
A silica content of 20% to 90% by weight,
The content of magnesia is 5-40% by weight,
The content of calcia is 5% by weight to 40% by weight.
上記無機繊維（７）は、例えば、
シリカの含有量が５０重量％〜９０重量％、
マグネシアの含有量が５重量％〜２５重量％、
カルシアの含有量が５重量％〜２５重量％である。
The inorganic fiber (7) is, for example,
Silica content of 50 wt% to 90 wt%,
The content of magnesia is 5 wt% to 25 wt%,
The content of calcia is 5% by weight to 25% by weight.
上記無機繊維（８）は、例えば、
シリカの含有量が３５重量％〜７１重量％、
マグネシアの含有量が１４重量％〜５１重量％、
ジルコニアの含有量が０．５重量％〜２６重量％、
酸化モリブデンの含有量が０．５重量％〜２３重量％である。
The inorganic fiber (8) is, for example,
A silica content of 35% to 71% by weight,
The content of magnesia is 14% to 51% by weight,
The content of zirconia is 0.5 wt% to 26 wt%,
The content of molybdenum oxide is 0.5 wt% to 23 wt%.
上記無機繊維（８）は、例えば、
シリカの含有量が４０重量％〜６６重量％、
マグネシアの含有量が１９重量％〜４６重量％、
ジルコニアの含有量が１重量％〜２１重量％、
酸化モリブデンの含有量が１重量％〜１８重量％である。
The inorganic fiber (8) is, for example,
The silica content is 40% to 66% by weight,
The content of magnesia is 19% to 46% by weight,
The content of zirconia is 1% to 21% by weight,
The content of molybdenum oxide is 1% by weight to 18% by weight.
シリカの含有量を１５重量％超、１８重量％以上又は２０重量％以上としてもよい。
アルカリ金属酸化物（Ｎａ２Ｏ、Ｌｉ２Ｏ等）、酸化Ｍｏの各々は含まれても含まれなくてもよい。これらはそれぞれ又は合計で、５重量％以下、３重量％以下、２重量％以下、１重量％以下又は０．５重量％以下とすることができる。
The content of silica may be more than 15% by weight, 18% by weight or more, or 20% by weight or more.
Each of alkali metal oxides (Na 2 O, Li 2 O, etc.) and oxidized Mo may or may not be included. These may be 5% by weight or less, 3% by weight or less, 2% by weight or less, 1% by weight or less, or 0.5% by weight or less, respectively or in total.
ＺｎＯ、Ｂ２Ｏ３、Ｐ２Ｏ５、ＳｒＯ、ＢａＯ、Ｃｒ２Ｏ３、Ｆｅ２Ｏ３、ＭｏＯ３の各々は含まれても含まれなくてもよい。これらはそれぞれ５重量％以下、３重量％以下、２重量％以下、１重量％以下又は０．５重量％以下とすることができる。 Each of ZnO, B 2 O 3 , P 2 O 5 , SrO, BaO, Cr 2 O 3 , Fe 2 O 3 , and MoO 3 may or may not be included. These may be 5% by weight or less, 3% by weight or less, 2% by weight or less, 1% by weight or less, or 0.5% by weight or less, respectively.
生体溶解性無機繊維は、ロックウール及びガラス繊維以外の無機繊維とすることができる。 The biosoluble inorganic fiber can be an inorganic fiber other than rock wool and glass fiber.
また、本発明で用いる生体溶解性無機繊維は通常短繊維であり、平均繊維長は１０ｍｍ〜１００ｍｍである。長繊維や連続繊維ではないとすることができる。 Moreover, the biosoluble inorganic fiber used in the present invention is usually a short fiber, and the average fiber length is 10 mm to 100 mm. It can be said that they are not long fibers or continuous fibers.
また、表面改質無機繊維は、好ましくは加熱処理されている。
加熱処理により、無機繊維を用いて製造する二次製品の収縮を抑制できる。
加熱処理により無機繊維は非晶質から結晶質へ変化するが、非晶質、結晶質のどちらの状態でもよく、非晶質、結晶質部分がそれぞれが混在している状態でもよい。
加熱温度は、例えば１００℃以上、３００℃以上、好ましくは、６００℃以上、８００℃以上、さらに好ましくは１０００℃以上、１２００℃以上、１３００℃以上、１４００℃以上でよく、６００℃〜１４００℃、さらに好ましくは、８００℃〜１２００℃、８００℃〜１０００℃である。
The surface-modified inorganic fiber is preferably heat-treated.
By the heat treatment, shrinkage of a secondary product manufactured using inorganic fibers can be suppressed.
Although the inorganic fiber changes from amorphous to crystalline by the heat treatment, it may be either amorphous or crystalline, and may be in a state where both amorphous and crystalline parts are mixed.
The heating temperature may be, for example, 100 ° C or higher, 300 ° C or higher, preferably 600 ° C or higher, 800 ° C or higher, more preferably 1000 ° C or higher, 1200 ° C or higher, 1300 ° C or higher, 1400 ° C or higher, and 600 ° C to 1400 ° C. More preferably, they are 800 degreeC-1200 degreeC, 800 degreeC-1000 degreeC.
本発明に用いる改質剤は、ケイ素及びその化合物、アルミニウム及びその化合物、カルシウム及びその化合物、マグネシウム及びその化合物、ジルコニウム及びその化合物、チタン及びその化合物、リン及びその化合物、鉄及びその化合物、シリカ及びその化合物、モリブデン及びその化合物、タングステン及びその化合物である。単独物質又は混合物として使用できる。 The modifier used in the present invention is silicon and its compound, aluminum and its compound, calcium and its compound, magnesium and its compound, zirconium and its compound, titanium and its compound, phosphorus and its compound, iron and its compound, silica And its compounds, molybdenum and its compounds, tungsten and its compounds. It can be used as a single substance or as a mixture.
ケイ素系改質剤として、ケイ素及びその化合物を用いることができ、例えばケイ素、コロイダルシリカ、ヒュームドシリカ等のシリカ、ケイ酸塩等を挙げられる。 Silicon and its compounds can be used as the silicon-based modifier, and examples thereof include silica such as silicon, colloidal silica, and fumed silica, and silicate.
アルミニウム系改質剤として、アルミニウム及びその化合物を用いることができ、例えば、アルミニウム、アルミナゾル、ヒュームドアルミナ、アルミナ粉末等のアルミナ、塩化アルミニウム、硫酸アルミニウム、硝酸アルミニウム、乳酸アルミニウム等のアルミニウム塩、水酸化アルミニウム等を挙げられる。 As the aluminum-based modifier, aluminum and its compounds can be used. For example, aluminum such as aluminum, alumina sol, fumed alumina, alumina powder, aluminum salts such as aluminum chloride, aluminum sulfate, aluminum nitrate, aluminum lactate, water Examples thereof include aluminum oxide.
マグネシウム系改質剤として、マグネシウム及びその化合物を用いることができ、例えば、マグネシウム、マグネシア、塩化マグネシウム、硝酸マグネシウム等のマグネシウム塩、水酸化マグネシウム等を挙げられる。 Magnesium and its compounds can be used as the magnesium-based modifier, and examples thereof include magnesium salts such as magnesium, magnesia, magnesium chloride, and magnesium nitrate, and magnesium hydroxide.
カルシウム系改質剤として、カルシウム及びその化合物を用いることができ、例えば、カルシウム、カルシア、塩化カルシウム、硫酸カルシウム、硝酸カルシウム等のカルシウム塩、水酸化カルシウム等を挙げられる。 Calcium and its compounds can be used as the calcium modifier, and examples thereof include calcium salts such as calcium, calcia, calcium chloride, calcium sulfate, and calcium nitrate, and calcium hydroxide.
ジルコニウム系改質剤として、ジルコニウム及びその化合物を用いることができ、例えば、ジルコニウム、ジルコニア、塩化ジルコニウム、硫酸ジルコニウム、硝酸ジルコニウム等のジルコニウム塩、水酸化ジルコニウム、ジルコン酸塩等を挙げられる。 Zirconium and its compounds can be used as the zirconium-based modifier, and examples thereof include zirconium salts such as zirconium, zirconia, zirconium chloride, zirconium sulfate and zirconium nitrate, zirconium hydroxide and zirconate.
チタン系改質剤として、チタン及びその化合物を用いることができ、例えば、チタニア、塩化チタン、硫酸チタン、硝酸チタン等のチタン塩、水酸化チタン、チタン酸塩等を挙げられる。 Titanium and its compounds can be used as the titanium modifier, and examples thereof include titanium salts such as titania, titanium chloride, titanium sulfate, and titanium nitrate, titanium hydroxide, titanate, and the like.
鉄系改質剤として、鉄及びその化合物を用いることができ、例えば、鉄、酸化鉄、塩化鉄、硝酸鉄、硫酸鉄などの鉄塩等を挙げられる。 Iron and its compounds can be used as the iron-based modifier, and examples thereof include iron salts such as iron, iron oxide, iron chloride, iron nitrate, and iron sulfate.
リン系改質剤として、リン及びその化合物を用いることができ、例えば、リン、酸化リン、リン酸塩等を挙げられる。 As the phosphorus-based modifier, phosphorus and its compounds can be used, and examples thereof include phosphorus, phosphorus oxide, and phosphate.
モリブデン系改質剤として、モリブデン及びその化合物を用いることができ、例えば、モリブデン、酸化モリブデン、二硫化モリブデン、二珪化モリブデン、モリブデン酸アンモニウム等のモリブデン酸塩等を挙げられる。 As the molybdenum-based modifier, molybdenum and a compound thereof can be used, and examples thereof include molybdenum, molybdenum oxide, molybdenum disulfide, molybdenum disilicide, and molybdate such as ammonium molybdate.
タングステン系改質剤として、タングステン及びその化合物を用いることができ、例えば、タングステン、酸化タングステン、二硫化タングステン、タングステン酸塩等を挙げられる。 Tungsten and its compounds can be used as the tungsten-based modifier, and examples thereof include tungsten, tungsten oxide, tungsten disulfide, and tungstate.
好ましい改質剤は、アルミナ、アルミニウム塩、マグネシウム塩、モリブデン、タングステン、酸化モリブデンである。
アルミナ又はアルミニウム塩と、マグネシウム塩の組み合わせが好ましい。
モリブデン、タングステン、又は酸化モリブデンが好ましい。
Preferred modifiers are alumina, aluminum salt, magnesium salt, molybdenum, tungsten, and molybdenum oxide.
A combination of an alumina or aluminum salt and a magnesium salt is preferred.
Molybdenum, tungsten, or molybdenum oxide is preferred.
改質剤の無機繊維表面への付着量は、本発明の効果が得られれば特に限定されないが、通常、表面改質無機繊維１００重量％に対し、０．１重量％〜５０重量％である。好ましくは０．５重量％〜４０重量％、より好ましくは０．８重量％〜３０重量％、さらに好ましくは１重量％〜２０重量％である。１０重量％以下とすることもできる。 The amount of the modifier adhering to the surface of the inorganic fiber is not particularly limited as long as the effect of the present invention is obtained, but is usually 0.1% by weight to 50% by weight with respect to 100% by weight of the surface modified inorganic fiber. . Preferably they are 0.5 weight%-40 weight%, More preferably, they are 0.8 weight%-30 weight%, More preferably, they are 1 weight%-20 weight%. It can also be 10 weight% or less.
本発明の表面改質無機繊維は、無機繊維を製造する際又は製造した後に、改質剤を付着させて製造できる。例えば、以下の方法を例示できる。
無機繊維からなるフリースに、改質剤を含む溶液又は分散液を付着させる。例えば、溶液又は分散液を塗布、スプレーするか、溶液又は分散液に浸漬する。
溶融した原料に、空気を吹き付けて、製糸する際、改質剤を空気と共に吹き付けて、無機繊維の表面に、前記改質剤を付着させる。
また、繊維を、開繊し、改質剤を添加する。その後、成形する。
加熱してもよいし、しなくてもよい。
The surface-modified inorganic fiber of the present invention can be produced by attaching a modifier when or after producing the inorganic fiber. For example, the following method can be illustrated.
A solution or dispersion containing a modifier is attached to a fleece made of inorganic fibers. For example, the solution or dispersion is applied and sprayed, or immersed in the solution or dispersion.
When air is blown to the melted raw material to produce a yarn, the modifier is blown together with air to adhere the modifier to the surface of the inorganic fiber.
Also, the fiber is opened and a modifier is added. Then, it shape | molds.
It may or may not be heated.
本発明の表面改質無機繊維から得られる成形体（ブランケット、ボード等）は、表面改質しない無機繊維からなる成形体に比べて、加熱収縮率が小さい。 A molded body (a blanket, a board, etc.) obtained from the surface-modified inorganic fiber of the present invention has a smaller heat shrinkage than a molded body composed of an inorganic fiber that is not surface-modified.
成形体の加熱収縮率は、実施例記載の方法で測定したとき、各温度（１０００℃、１４００℃）において、好ましくは３０％以下、２０％以下、さらに好ましくは１０％以下、最も好ましくは５％以下である。 The heat shrinkage ratio of the molded body is preferably 30% or less, 20% or less, more preferably 10% or less, and most preferably 5 at each temperature (1000 ° C., 1400 ° C.) as measured by the method described in the Examples. % Or less.
本発明の繊維から、様々な二次製品が得られる。例えば、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、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等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、これら定形品、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。 Various secondary products are obtained from the fibers of the present invention. For example, bulks, blankets, blocks, ropes, yarns, textiles, fibers coated with surfactants, shotless bulks that reduce or eliminate shots (unfibrinated products), boards that are manufactured using solvents such as water, and molds , Regular products such as paper, felt and wet felt. 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 these regular and irregular shaped products 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等の補強用繊維、耐熱材、耐火材の補強繊維、接着剤、コート材等の補強繊維）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, filling material, 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 holding materials, various fiber reinforced composite materials (for example, fiber reinforced cement, fiber reinforced plastic and other reinforcing fibers, heat resistance Materials, reinforcing fibers such as refractory materials, reinforcing fibers such as adhesives and coating materials) and the like.
実施例１〜７３，比較例１〜１５
表１〜７に示す組成を有する繊維からなるフリースを製造し、表１〜７に示す改質剤を含む液に浸し、その後乾燥し、表中、付着率は表面改質無機繊維における改質剤の量（重量％）である。改質剤の量は、改質剤に含まれる各元素を酸化物換算して示した。
比較例では、改質剤を含む液に浸さなかった。
得られたフリースについて、以下の方法で加熱収縮率を評価した。結果を表１〜７に示す。
Examples 1 to 73, Comparative Examples 1 to 15
The fleece which consists of a fiber which has a composition shown in Tables 1-7 is manufactured, it is immersed in the liquid containing the modifier shown in Tables 1-7, and it dries after that, and adhesion rate is modification in surface modification inorganic fiber in the table. The amount (% by weight) of the agent. The amount of the modifier is shown by converting each element contained in the modifier into an oxide.
In the comparative example, it was not immersed in the liquid containing the modifier.
About the obtained fleece, the heat shrinkage rate was evaluated by the following method. The results are shown in Tables 1-7.
フリースからサンプル（１４０ｍｍ×５０ｍｍ×１０ｍｍ）を切り出し、１０００℃又は１４００℃で８時間焼成した。
サンプル表面に白金ピンを２点以上打ち込み、その白金ピン間の距離を加熱前後で測定し、その寸法変化率を加熱収縮率とした。
A sample (140 mm × 50 mm × 10 mm) was cut from the fleece and baked at 1000 ° C. or 1400 ° C. for 8 hours.
Two or more platinum pins were driven into the sample surface, the distance between the platinum pins was measured before and after heating, and the dimensional change rate was defined as the heat shrinkage rate.
実施例７４〜８７，比較例１６〜２２
表８〜１０に示す組成を有する繊維を、水中で開繊し、表８〜１０に示す改質剤を所定量添加した。凝集剤でフロックを形成した後、脱水し、成形し、乾燥してサンプル（１５０ｍｍ×１２０ｍｍ×２５ｍｍ）を得た。
比較例では、改質剤は添加しなかった。
得られたサンプルについて、実施例１と同様にして評価した。結果を表８〜１０に示す。
Examples 74-87, Comparative Examples 16-22
Fibers having the compositions shown in Tables 8 to 10 were opened in water, and a predetermined amount of modifiers shown in Tables 8 to 10 were added. A floc was formed with a flocculant, then dehydrated, molded and dried to obtain a sample (150 mm × 120 mm × 25 mm).
In the comparative example, no modifier was added.
The obtained sample was evaluated in the same manner as in Example 1. The results are shown in Tables 8-10.
実施例８８〜１０２，比較例２３〜３１
表１１〜１５に示す組成を有する繊維からなるフリースを製造した。その際、ノズルから、製繊と同時に、表１１〜１５に示す改質剤を含む液をスプレー噴霧した。
比較例では、改質剤は吹き付けなかった。
得られたフリースについて、実施例１と同様にして評価した。結果を表１１〜１５に示す。
Examples 88-102, Comparative Examples 23-31
The fleece which consists of a fiber which has a composition shown to Tables 11-15 was manufactured. At that time, the liquid containing the modifiers shown in Tables 11 to 15 was sprayed from the nozzle simultaneously with fiber formation.
In the comparative example, the modifier was not sprayed.
The obtained fleece was evaluated in the same manner as in Example 1. The results are shown in Tables 11-15.
さらに、得られた繊維について、以下の方法で溶解速度定数を求めた。
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及びｐＨ７．５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た。貯めた濾液を２４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た。測定元素は主要元素であるＳｉ、Ａｌ、Ｍｇ、Ｃａとした。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）に換算した。
Furthermore, the dissolution rate constant was calculated | required with the following method about the obtained fiber.
The fiber was placed on a membrane filter, pH 4.5 and pH 7.5 physiological saline was dropped on the fiber with a micropump, and the filtrate that passed through the fiber and filter was stored in a container. The accumulated filtrate was taken out after 24 hours, and the eluted components were quantified with an ICP emission spectrometer. The measurement elements were Si, Al, Mg, and Ca, which are main elements. The fiber diameter was measured and converted to a dissolution rate constant k (unit: ng / cm 2 · h) which is the amount of elution per unit surface area / unit time.
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 (19)
ＳｉＯ２とＺｒＯ２とＡｌ２Ｏ３とＴｉＯ２との合計 ５０重量％〜８２重量％
アルカリ金属酸化物とアルカリ土類金属酸化物との合計 １８重量％〜５０重量％ The surface-modified inorganic fiber according to claim 1, wherein the biosoluble inorganic fiber has the following composition.
The total of SiO 2 , ZrO 2 , Al 2 O 3 and TiO 2 50 wt% to 82 wt%
Total of alkali metal oxides and alkaline earth metal oxides 18% to 50% by weight
シリカ、アルミナから選択される１以上と、
マグネシア、カルシア、ジルコニアから選択される１以上を、主成分として含む無機繊維である請求項１記載の表面改質無機繊維。 The biosoluble inorganic fiber is
One or more selected from silica and alumina;
The surface-modified inorganic fiber according to claim 1, which is an inorganic fiber containing one or more selected from magnesia, calcia, and zirconia as a main component.
シリカ、アルミナから選択される１以上 ０．３重量％〜９０重量％
マグネシア、カルシア、ジルコニアから選択される１以上 １０重量％〜６０重量％ The surface-modified inorganic fiber according to claim 3, wherein the biosoluble inorganic fiber has the following composition.
1 or more selected from silica and alumina 0.3% by weight to 90% by weight
1 or more selected from magnesia, calcia, zirconia 10 wt% to 60 wt%
シリカ、アルミナ、マグネシア、カルシアを、主成分として含む請求項１又は２記載の表面改質無機繊維。 The biosoluble inorganic fiber is
The surface-modified inorganic fiber according to claim 1 or 2, comprising silica, alumina, magnesia, and calcia as main components.
前記生体溶解性無機繊維が、
シリカ、マグネシア、ジルコニアを、主成分として含む表面改質無機繊維（ただし、コロイダルシリカを含む溶液又は分散液を付着させたブランケットに含まれる表面改質無機繊維は除く）。 On the surface of the biosoluble inorganic fiber, silicon and its compound, aluminum and its compound, calcium and its compound, magnesium and its compound, zirconium and its compound, titanium and its compound, phosphorus and its compound, iron and its compound, molybdenum And one or more modifiers selected from tungsten and its compounds are attached, and
The biosoluble inorganic fiber is
Surface-modified inorganic fibers containing silica, magnesia and zirconia as main components (excluding surface-modified inorganic fibers contained in a blanket to which a solution or dispersion containing colloidal silica is attached) .
シリカ、アルミナ、及びカルシア又はマグネシアを、主成分として含む請求項１又は２記載の表面改質無機繊維。 The biosoluble inorganic fiber is
The surface-modified inorganic fiber according to claim 1 or 2, comprising silica, alumina, and calcia or magnesia as main components.
シリカ、マグネシアを、主成分として含む請求項１又は２記載の表面改質無機繊維。 The biosoluble inorganic fiber is
The surface-modified inorganic fiber according to claim 1 or 2, comprising silica and magnesia as main components.
シリカ、カルシアを、主成分として含む請求項１又は２記載の表面改質無機繊維。 The biosoluble inorganic fiber is
The surface-modified inorganic fiber according to claim 1 or 2, comprising silica and calcia as main components.
シリカ、マグネシア、カルシアを、主成分として含む請求項１又は２記載の表面改質無機繊維。 The biosoluble inorganic fiber is
The surface-modified inorganic fiber according to claim 1 or 2, comprising silica, magnesia, and calcia as main components.
ロックウール及びガラス繊維ではない請求項１又は２記載の表面改質無機繊維。 The biosoluble inorganic fiber is
The surface-modified inorganic fiber according to claim 1 or 2, which is not rock wool or glass fiber.
生体溶解性無機繊維を、前記改質剤を含む溶液又は分散液に浸し、
前記生体溶解性無機繊維の表面に、前記改質剤を付着させる表面改質無機繊維の製造方法。 A method for producing a surface-modified inorganic fiber according to any one of claims 1 to 16,
Immerse the biosoluble inorganic fiber in a solution or dispersion containing the modifier,
A method for producing a surface-modified inorganic fiber, wherein the modifying agent is attached to the surface of the biosoluble inorganic fiber.
溶融した無機繊維原料に、空気を吹き付けて、生体溶解性無機繊維を製造する方法において、
前記改質剤を、共に吹きつけて、前記生体溶解性無機繊維の表面に、前記改質剤を付着させる表面改質無機繊維の製造方法。 A method for producing a surface-modified inorganic fiber according to any one of claims 1 to 16,
In the method for producing biosoluble inorganic fibers by blowing air to the molten inorganic fiber raw material,
The manufacturing method of the surface modification inorganic fiber which sprays together the said modifier and adheres the said modifier to the surface of the said biosoluble inorganic fiber.
The secondary product or composite material manufactured using the surface modification inorganic fiber in any one of Claims 1-16.
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