JP2002266169A - Heat-resistant inorganic fiber and inorganic fiber product - Google Patents
Heat-resistant inorganic fiber and inorganic fiber productInfo
- Publication number
- JP2002266169A JP2002266169A JP2001391271A JP2001391271A JP2002266169A JP 2002266169 A JP2002266169 A JP 2002266169A JP 2001391271 A JP2001391271 A JP 2001391271A JP 2001391271 A JP2001391271 A JP 2001391271A JP 2002266169 A JP2002266169 A JP 2002266169A
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- Prior art keywords
- inorganic fiber
- heat
- weight
- resistant inorganic
- fibers
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- Inorganic Fibers (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、耐熱性無機繊維及
び無機繊維製品に関し、例えば、１２００℃以上の耐熱
性を有し、さらに生体に溶解しやすい耐熱性無機繊維お
よびその繊維を使用した無機繊維製品に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-resistant inorganic fiber and an inorganic fiber product, for example, a heat-resistant inorganic fiber having a heat resistance of 1200.degree. Related to textile products.
【０００２】[0002]
【従来の技術】耐火断熱材として、また摩擦材の充填材
として、広く無機繊維が使用されている。無機繊維は、
そのまま、あるいはブランケット、ブロック、ペーパ
ー、ボード等の無機繊維製品に加工して用いられる。2. Description of the Related Art Inorganic fibers are widely used as refractory heat insulating materials and as fillers for friction materials. Inorganic fibers are
It is used as it is or after being processed into inorganic fiber products such as blankets, blocks, papers and boards.
【０００３】これらの無機繊維は、人の健康の観点か
ら、生体に溶解しやすいことが望ましいとされてきた。
そして生理食塩水に溶解する無機繊維が多数提案されて
いる。例えば、特表平８−５０６５６１号には、添加成
分としてＡｌ2Ｏ3、ＺｒＯ2、ＴｉＯ2を含むＣａＯ−Ｍ
ｇＯ−ＳｉＯ2繊維の生理食塩水への溶解性および耐熱
性が記載されている。[0003] From the viewpoint of human health, it has been desirable that these inorganic fibers be easily soluble in living bodies.
Many inorganic fibers that dissolve in physiological saline have been proposed. For example, Japanese Patent Publication No. Hei 8-506561 discloses a CaO-M containing Al 2 O 3 , ZrO 2 , and TiO 2 as additive components.
gO-SiO 2 solubility and heat resistance of the fiber to the saline is described.
【０００４】また特表平１０−５１２２３２号には、シ
リカ、マグネシアを必須成分とし、かつジルコニアを任
意に含むガラス繊維が記載されている。[0004] JP-T-10-512232 describes a glass fiber containing silica and magnesia as essential components and optionally containing zirconia.
【０００５】[0005]
【発明が解決しようとする課題】しかし、これらの無機
繊維は、比較的生体に溶解しやすい繊維としての特性は
有するものの、高温での耐熱性にいまだ問題が残されて
いる。However, although these inorganic fibers have properties as fibers that are relatively easily dissolved in living bodies, there still remains a problem in heat resistance at high temperatures.
【０００６】特表平８−５０６５６１号および特表平１
０−５１２２３２号に提案された繊維は、共に非晶質で
あり不安定である。高温に加熱されると、結晶を析出し
て収縮する。この理由により、耐熱性は組成によって制
限されていた。JP-T 8-506561 and JP-T-1
The fibers proposed in 0-512232 are both amorphous and unstable. When heated to high temperatures, crystals precipitate and shrink. For this reason, the heat resistance has been limited by the composition.
【０００７】本発明の目的は、無機繊維及び無機繊維製
品の耐熱性を改善することである。An object of the present invention is to improve the heat resistance of inorganic fibers and inorganic fiber products.
【０００８】[0008]
【課題を解決するための手段】本発明は、繊維に微結晶
を含ませることにより、同じ組成の無機繊維であっても
耐熱性を改善したものである。According to the present invention, the heat resistance of inorganic fibers having the same composition is improved by incorporating fine crystals into the fibers.
【０００９】本発明の解決手段を例示すれば、請求項１
〜５に記載の耐熱性無機繊維及びこれらの繊維を使用し
たブランケット、ブロック、ぺーパー、ボード等の無機
繊維製品である。An example of the solution of the present invention will be described below.
And inorganic fiber products using these fibers, such as blankets, blocks, papers and boards.
【００１０】[0010]
【発明の実施の形態】本発明は、シリカを主成分とする
無機繊維において、非晶質繊維に析出する結晶に注目し
て研究した結果、結晶が微結晶であれば繊維の取り扱い
性を維持したまま、高温での寸法安定性に優れ、すなわ
ち耐熱性に優れ、且つ生体に溶解しやすい特性を有する
ことを見いだして完成した。BEST MODE FOR CARRYING OUT THE INVENTION The present invention has been studied by focusing on crystals precipitated on amorphous fibers in inorganic fibers containing silica as a main component. As a result, they completed the process by finding that they have excellent dimensional stability at high temperatures, that is, they have excellent heat resistance and are easily dissolved in living bodies.
【００１１】生体溶解性は、シリカガラスにカルシアや
マグネシアなどの網目修飾成分を添加することにより、
シリカガラスの構造が変化し非架橋酸素が増加すること
により増大すると考えられている。The biosolubility can be improved by adding a network modifying component such as calcia or magnesia to silica glass.
It is believed that the increase is caused by a change in the structure of the silica glass and an increase in non-crosslinking oxygen.
【００１２】一方、マグネシア、カルシアなどのアルカ
リ土類金属は、シリカ繊維の耐熱性を低下させやすい。
従って、生体溶解性は、アルカリ土類金属を添加するこ
とによって得ている一方、耐熱性は、シリカガラスで得
ている。On the other hand, alkaline earth metals such as magnesia and calcia tend to lower the heat resistance of silica fibers.
Therefore, biosolubility is obtained by adding an alkaline earth metal, while heat resistance is obtained by silica glass.
【００１３】従って、シリカの含有量は、５８重量％以
上が好ましい。特に、シリカ−マグネシア系繊維では、
シリカの含有量は、６５％以上が好ましい。これよりも
少ないと、耐熱性が低下する。また、シリカ含有量が、
８６％以上になると、製造の際に、原料の溶融が困難と
なり、繊維化しにくくなる。Therefore, the content of silica is preferably at least 58% by weight. In particular, silica-magnesia fiber,
The content of silica is preferably 65% or more. If it is less than this, the heat resistance decreases. Also, the silica content,
If it is 86% or more, it becomes difficult to melt the raw materials during production, and it is difficult to produce fibers.
【００１４】ジルコニアは、結晶の成長を抑制する働き
があり、耐熱性を改善できる。Zirconia has a function of suppressing crystal growth and can improve heat resistance.
【００１５】これらから、本発明の１つの実施形態によ
る耐熱性無機繊維の組成は、ＳｉＯ 2が５８〜８０重量
％であり、ＣａＯが１〜４０重量％であり、ＭｇＯが０
〜１５重量％であり、Ａｌ2Ｏ3が０〜３重量％であり、
ＺｒＯ2が０〜１１重量％であり、本発明の他の実施形
態による耐熱性無機繊維の組成は、ＳｉＯ2が６５〜８
６重量％であり、ＭｇＯが１４〜３５重量％であり、Ａ
ｌ2Ｏ3が０〜３重量％であり、ＺｒＯ2を０〜１１重量
％であることが好ましい。From these, according to one embodiment of the present invention,
The composition of the heat-resistant inorganic fiber is SiO TwoIs 58-80 weight
%, CaO is 1 to 40% by weight, and MgO is 0%.
~ 15% by weight, AlTwoOThreeIs 0 to 3% by weight,
ZrOTwoIs 0 to 11% by weight, which is another embodiment of the present invention.
The composition of the heat-resistant inorganic fiber according to the state is SiO 2TwoIs 65-8
6% by weight, 14-35% by weight of MgO,
lTwoOThreeIs 0 to 3% by weight, and ZrOTwo0 to 11 weight
%.
【００１６】本発明では、無機繊維の組成として耐熱性
を低下させやすいマグネシア、カルシアを使用しても、
５００Ａ（オングストローム）以下の微結晶を短時聞で
析出させれば、生体溶解性を維持したまま、耐熱性を向
上できる。In the present invention, even if magnesia or calcia which easily lowers heat resistance is used as the composition of the inorganic fiber,
If microcrystals of 500 A (angstrom) or less are precipitated in a short time, heat resistance can be improved while maintaining biosolubility.
【００１７】結晶サイズが、５００Ａ（オングストロー
ム）を越えると、繊維が脆くなって繊維の取り扱い性が
低下する。If the crystal size exceeds 500 A (angstrom), the fibers become brittle and the handling properties of the fibers deteriorate.
【００１８】非晶質繊維から結晶を析出させる条件は、
８００℃〜１１００℃で３分間から５０分間加熱処理す
るのが好ましい。より好ましくは、９００℃〜１０００
℃で５分間から１０分間加熱処理するのがよい。加熱温
度が、８００℃より低いと結晶が析出しがたい。１１０
０℃より高温では、析出する結晶のサイズが過大になり
取り扱い性に劣る。The conditions for precipitating crystals from the amorphous fibers are as follows:
The heat treatment is preferably performed at 800 ° C. to 1100 ° C. for 3 to 50 minutes. More preferably, 900 ° C to 1000 ° C
The heat treatment is preferably performed at 5 ° C. for 5 to 10 minutes. When the heating temperature is lower than 800 ° C., crystals are difficult to precipitate. 110
If the temperature is higher than 0 ° C., the size of the precipitated crystals becomes excessively large and the handling properties are poor.
【００１９】析出する結晶は、組成により異なるが、例
えば、ウオラストナイト（ＣａＯ・ＳｉＯ2）、偽珪灰
石（ＣａＯ・ＳｉＯ2）、オージャイト（ディオプサイ
ド）（ＣａＯ・ＭｇＯ・２ＳｉＯ2）、エンスタタイト
（ＭｇＯ・ＳｉＯ2）などが耐熱性および健康安全性の
点から好ましい。[0019] The precipitated crystals varies depending on the composition, for example, wollastonite (CaO · SiO 2), false wollastonite (CaO · SiO 2), Ojaito (diopside) (CaO · MgO · 2SiO 2 ), Enstatite (MgO.SiO 2 ) is preferred from the viewpoint of heat resistance and health safety.
【００２０】無機繊維には通常Ｆｅ、Ｎａ、Ｋ等の不純
物が０.１〜０．２％程度含有されている。この不純物
は、無機繊維の耐熱性を低下させる。特にＮａとＫは大
きく耐熱性を低下させる。ＮａとＫの合計の含有量は、
少ないのが好ましく、５００ｐｐｍ以下が好ましい。Ｎ
ａとＫの合計の含有量を５００ｐｐｍ以下に制限するこ
とにより、耐熱性に優れた繊維が得られる。さらに、珪
肺の原因の一つである遊離珪酸であるクリストバライト
を析出しにくくする事が出来る。The inorganic fibers usually contain about 0.1 to 0.2% of impurities such as Fe, Na and K. These impurities reduce the heat resistance of the inorganic fibers. In particular, Na and K greatly reduce heat resistance. The total content of Na and K is
It is preferably as low as possible, and preferably 500 ppm or less. N
By limiting the total content of a and K to 500 ppm or less, a fiber having excellent heat resistance can be obtained. Further, it is possible to make it difficult to deposit cristobalite, which is free silicic acid, which is one of the causes of silicosis.
【００２１】無機繊維製品としては、ブランケット、ブ
ロック、ペーパー、ボードなどに加工した製品がよく知
られている。これらの製品の材料として、本発明の耐熱
性無機繊維を使用することが出来る。As inorganic fiber products, products processed into blankets, blocks, papers, boards and the like are well known. The heat-resistant inorganic fiber of the present invention can be used as a material for these products.
【００２２】[0022]
【実施例】種々の配合原料を溶融し、その細流を空気ジ
ェットで吹き飛ばして、非晶質の繊維を得た。この繊維
をブランケットに形成し、所定の条件で加熱処理して微
結晶を析出させ、その特性を試験した。EXAMPLES Various blended raw materials were melted, and their rivulets were blown off with an air jet to obtain amorphous fibers. The fiber was formed into a blanket and heat-treated under predetermined conditions to precipitate microcrystals, and the properties were tested.
【００２３】ブランケットに使用した繊維の組成、加熱
処理条件、加熱収縮率、生理食塩水への溶解性などを表
１に示す。Table 1 shows the fiber composition, heat treatment conditions, heat shrinkage, and solubility in physiological saline used for the blanket.
【００２４】[0024]
【表１】 表１の析出結晶は、Ｘ線解析により鉱物名を同定した。
又、結晶サイズは、Ｘ線回折チャートから半値幅を測定
して求めた。[Table 1] The precipitated crystals in Table 1 were identified by mineral name by X-ray analysis.
The crystal size was determined by measuring the half width from an X-ray diffraction chart.
【００２５】取り扱い性は、加熱処理後の厚さ２５ｍｍ
のブランケットを直径１５ｃｍの棒に巻き取り、巻き取
りできるものを良（ただし表１の実施例６は巻取が可能
であるが困難である）とし、巻き取り出来ないものを悪
として区別した。The handleability is 25 mm in thickness after heat treatment.
Was rolled up into a rod having a diameter of 15 cm, and those that could be wound up were classified as good (however, Example 6 in Table 1 could be rolled up but difficult), and those that could not be rolled up were classified as bad.
【００２６】クリストバライトの析出は、繊維を１１０
０℃で２４時間加熱し、その後粉末にして、Ｘ線回折チ
ャートを取り、そのピーク高さを測定した。実施例１〜
６および比較例１〜３に、一番高いピーク高さを１０と
して示す。The precipitation of cristobalite causes the fibers to reach 110
The mixture was heated at 0 ° C. for 24 hours, then made into a powder, an X-ray diffraction chart was taken, and the peak height was measured. Example 1
6 and Comparative Examples 1 to 3 show that the highest peak height is 10.
【００２７】生理食塩水溶解性は、２００メッシュの篩
を通過するまで粉砕した繊維１ｇを秤量し、３００ｍｌ
の三角フラスコに入れ、生理食塩水１５０ｍｌを加え、
ホットプレート付スターラーに設置し、４０℃で４８時
間、回転数２００ｒｐｍで撹拌する。撹拌後、フラスコ
中の繊維を秤量し、処理前後の重量変化から溶解率を求
めた。溶解率の大きいほど生体に溶解し易い。The solubility in physiological saline was determined by weighing 1 g of ground fiber until it passed through a 200-mesh sieve, and measuring 300 ml.
Into an Erlenmeyer flask, add 150 ml of physiological saline,
Place on a stirrer with a hot plate and stir at 40 ° C. for 48 hours at 200 rpm. After stirring, the fibers in the flask were weighed, and the dissolution rate was determined from the change in weight before and after the treatment. The higher the dissolution rate, the easier it is to dissolve in the living body.
【００２８】実施例２と比較例３を比較すると、組成が
同じであり、実施例２が加熱処理しているのに対して、
比較例３は加熱処理がされていない。この結果、組成が
同じでも、微結晶の析出により耐熱性が改善されること
が明らかである。A comparison between Example 2 and Comparative Example 3 shows that the compositions are the same.
In Comparative Example 3, no heat treatment was performed. As a result, it is clear that even if the composition is the same, the heat resistance is improved by the precipitation of microcrystals.
【００２９】[0029]
【発明の効果】本発明の耐熱性無機繊維は、耐熱性およ
び生体溶解性を兼ね備えている。従って、生体に害の少
ない耐火断熱材として、従来のアルミナシリカ繊維と同
様に使用できる。また、クリストバライトが析出しにく
いので、健康に対して、より安全に使用できる。The heat-resistant inorganic fiber of the present invention has both heat resistance and biosolubility. Therefore, it can be used as a fire-resistant heat insulating material with little harm to the living body, similarly to the conventional alumina silica fiber. Also, since cristobalite does not easily precipitate, it can be used more safely for health.
【００３０】耐火断熱材の用途以外にも、例えば、摩擦
材として、健康被害の少ない無機繊維として使用でき
る。In addition to the use as a fire-resistant heat insulating material, it can be used, for example, as a friction material and as an inorganic fiber with little health damage.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 大宮 修史 東京都中央区日本橋久松町４番４号 糸重 ビル 東芝モノフラックス株式会社内 Ｆターム(参考） 4L037 AT05 CS20 FA05 PA31 PF07 UA06 UA20 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Osamu Omiya 4-4 Nihonbashi Hisamatsucho, Chuo-ku, Tokyo Itoishi Building Toshiba Monoflux Corporation F-term (reference) 4L037 AT05 CS20 FA05 PA31 PF07 UA06 UA20
Claims (6)
ａＯが１〜４０重量％であり、ＭｇＯが０〜１５重量％
であり、Ａｌ2Ｏ3が０〜３重量％であり、ＺｒＯ2が０
〜１１重量％であり、ウオラストナイト、偽珪灰石、オ
ージャイトのいずれかの微結晶を含むことを特徴とする
耐熱性無機繊維。1. The method according to claim 1, wherein the content of SiO 2 is from 58 to 80% by weight,
aO is 1 to 40% by weight, and MgO is 0 to 15% by weight.
By and are Al 2 O 3 0 to 3 wt%, ZrO 2 0
A heat-resistant inorganic fiber, which is about 11% by weight and contains microcrystals of wollastonite, pseudowollastonite, and augite.
ｇＯが１４〜３５重量％であり、Ａｌ2Ｏ3が０〜３重量
％であり、ＺｒＯ2を０〜１１重量％であ り、エンス
タタイトの微結晶を含むことを特徴とする耐熱性無機繊
維。2. The composition according to claim 1, wherein the content of SiO 2 is 65 to 86% by weight.
gO is 14-35 wt%, Al 2 O 3 is 0 to 3 wt%, the ZrO 2 Ri 0-11 wt% der, heat-resistant inorganic, characterized in that it comprises crystallites of enstatite fiber.
ｐｍ以下であることを特徴とする請求項１又は２に記載
の耐熱性無機繊維。3. The total of Na and K as impurities is 500 p.
3. The heat-resistant inorganic fiber according to claim 1, wherein the heat-resistant inorganic fiber is at most pm.
ローム）以下であることを特徴とする請求項１乃至３の
いずれか１項に記載の耐熱性無機繊維。4. The heat-resistant inorganic fiber according to claim 1, wherein the size of the microcrystal is 500 A (angstrom) or less.
分間熱処理をして微結晶を析出させたことを特徴とする
請求項１乃至４のいずれか１項に記載の耐熱性無機繊
維。5. A temperature of 800 ° C. to 1100 ° C. for 3 minutes to 50 ° C.
The heat-resistant inorganic fiber according to any one of claims 1 to 4, wherein heat treatment is performed for a minute to precipitate microcrystals.
無機繊維からなることを特徴とする無機繊維製品。6. An inorganic fiber product comprising the inorganic fiber according to any one of claims 1 to 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001391271A JP2002266169A (en) | 2000-12-27 | 2001-12-25 | Heat-resistant inorganic fiber and inorganic fiber product |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000398239 | 2000-12-27 | ||
| JP2000-398239 | 2000-12-27 | ||
| JP2001391271A JP2002266169A (en) | 2000-12-27 | 2001-12-25 | Heat-resistant inorganic fiber and inorganic fiber product |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002266169A true JP2002266169A (en) | 2002-09-18 |
Family
ID=26606872
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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| JP2005515307A (en) * | 2002-01-10 | 2005-05-26 | ユニフラックス コーポレイション | High temperature resistant glassy inorganic fiber |
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| JP2006089881A (en) * | 2004-09-24 | 2006-04-06 | Saint-Gobain Tm Kk | Inorganic fiber and method for producing the same |
| JP2006152468A (en) * | 2004-11-26 | 2006-06-15 | Saint-Gobain Tm Kk | Inorganic fiber and method for producing the same |
| JP2006282404A (en) * | 2005-03-31 | 2006-10-19 | Nichias Corp | Monolithic heat insulating material composition |
| JP2006306713A (en) * | 2005-03-31 | 2006-11-09 | Nichias Corp | Indeterminate heat insulating material composition |
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