WO2012090455A1 - 生体溶解性無機繊維 - Google Patents
生体溶解性無機繊維 Download PDFInfo
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- WO2012090455A1 WO2012090455A1 PCT/JP2011/007205 JP2011007205W WO2012090455A1 WO 2012090455 A1 WO2012090455 A1 WO 2012090455A1 JP 2011007205 W JP2011007205 W JP 2011007205W WO 2012090455 A1 WO2012090455 A1 WO 2012090455A1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
- C04B35/62231—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on oxide ceramics
- C04B35/6224—Fibres based on silica
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- 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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- 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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Definitions
- the present invention relates to an alkaline earth silicate fiber that is soluble in physiological saline.
- Inorganic fibers are lightweight, easy to handle, and excellent in heat resistance, and thus are used as, for example, heat-resistant sealing materials.
- problems have recently been pointed out that inorganic fibers are inhaled into the human body and enter the lungs.
- biosoluble inorganic fibers have been developed that do not cause problems even when inhaled by the human body, or are unlikely to occur (for example, Patent Documents 1 and 2).
- Patent Document 2 discloses many fibers excellent in fire resistance and biosolubility, but has a problem in fiber quality. In particular, it is described that when Al 2 O 3 increases, the biosolubility is lowered and the fiber quality is adversely affected. Biosoluble inorganic fibers have a high viscosity of the raw material, and could not be spun unless the temperature was extremely high. Therefore, it was difficult to obtain a fiber having a small fiber diameter. In addition, there is a problem that it is difficult to mold if the water solubility of the fiber is high.
- An object of the present invention is to provide an inorganic fiber excellent in fire resistance and biosolubility.
- ZrO 2 , R 2 O 3 R is selected from Sc, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y or a mixture thereof.
- R is selected from Sc, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y or a mixture thereof.
- each of the alkali metal oxides is 0.2% by weight or less
- the total of SiO 2 , CaO, MgO and Al 2 O 3 is 99% by weight or more.
- the inorganic fiber according to 1 or 2 wherein TiO 2 , ZnO, B 2 O 3 , and P 2 O 5 are each 0.1% by weight or less. 4). 4. The inorganic fiber according to any one of 1 to 3, wherein Al 2 O 3 is 1.1 to 1.95% by weight. 5. The inorganic fiber according to any one of 1 to 3, wherein Al 2 O 3 is 2.0 to 3.4% by weight. 6). 4. The inorganic fiber according to any one of 1 to 3, wherein Al 2 O 3 is 1.3 to 2.5% by weight. 7. The inorganic fiber according to any one of 1 to 6, wherein SiO 2 is 71.25% by weight or more. 8). An inorganic fiber having the following composition.
- ZrO 2 , R 2 O 3 R is selected from Sc, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y or a mixture thereof. Each) is 0.1% by weight or less
- the total of SiO 2 , CaO, MgO and Al 2 O 3 is 99% by weight or more. 9.
- the fiber of the present invention has the following composition. SiO 2 71-80% by weight CaO 18-27 wt% MgO 0-3 wt% Al 2 O 3 1.1 to 3.4% by weight
- Fibers of the present invention typically do not contain ZrO 2.
- ZrO 2 is 0.1% by weight or less or less than 0.1% by weight.
- the fibers of the present invention are usually R 2 O 3 (R is Sc, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y or mixtures thereof. Not selected).
- R 2 O 3 is 0.1% by weight or less or less than 0.1% by weight.
- Alkali metal oxides (K 2 O, Na 2 O, Li 2 O, etc.) may or may not be contained, and each or the total amount of the alkali metal oxides is 0.2% by weight or less, 0.15 It can be less than wt% or less than 0.1 wt%. Each or all of the alkali metal oxides may be contained in an amount exceeding 0.01% by weight, 0.05% by weight or more, or 0.08% by weight or more. K 2 O may or may not be contained, and may be 0.2% by weight or less, 0.15% by weight or less, or 0.1% by weight or less. K 2 O may be contained more than 0.01% by weight, 0.05% by weight or more, or 0.08% by weight or more.
- Na 2 O may or may not be contained, and may be 0.2% by weight or less, 0.15% by weight or less, or 0.1% by weight or less. Na 2 O may be contained more than 0.01% by weight, 0.05% by weight or more, or 0.08% by weight or more.
- Fibers of the present invention typically do not contain TiO 2. Moreover, each of ZnO, B 2 O 3 , P 2 O 5 , SrO, BaO, and Cr 2 O 3 is usually not included. SrO, P 2 O 5 , BaO, and Cr 2 O 3 may be contained by 0.1 wt% or less or less than 0.1 wt%. Fe 2 O 3 may be contained in an amount of 0.1 to 0.3% by weight.
- the total of SiO 2 , CaO, MgO, and Al 2 O 3 is 99% by weight or more, and can be 99.5% by weight or more or 99.7% by weight or more.
- Fe 2 O 3 the total of SiO 2 , CaO, MgO, Al 2 O 3 and Fe 2 O 3 is 99.7% by weight or more, 99.8% by weight or more, 99.9% by weight or more, or It can be 100% by weight.
- the SiO 2 content is 71 to 80% by weight, the heat resistance is excellent. There is a possibility that the amount of cristobalite carcinogenic substance formed after heating the SiO 2 is too much increases. Preferably it is 71 to 77% by weight, more preferably 71 to 76% by weight.
- the biosolubility is excellent and the product tensile strength is high. The amount is preferably 20 to 27% by weight, more preferably 21 to 26% by weight, still more preferably 23 to 26% by weight.
- the MgO content is 0 to 3% by weight, the biosolubility is excellent. When there is too much MgO, there exists a possibility that biological solubility may deteriorate after a heating. Preferably, it is 0 to 1% by weight. Usually present in excess of 0% by weight.
- the fiber has an appropriate water solubility without impairing the fiber quality, and is easy to process.
- it is 1.3 to 3.0% by weight.
- the amount of Al 2 O 3 can be 1.3 to 1.95% by weight or 1.4 to 1.7% by weight. Further, the amount of Al 2 O 3 can be 1.5 to 3 or 2 to 3% by weight.
- an alkali metal oxide may be contained by 0.2% by weight or more (for example, 0.2 to 1.5% by weight).
- the fiber of the present invention has excellent biosolubility due to having the above composition, and especially the biosolubility increases after heating.
- Inorganic fibers such as those of the present invention are frequently used as heat insulating materials. Having biosolubility before heating is less likely to impair the health of the operator during manufacture, installation, and the like. Having biosolubility after heating is less likely to impair the health of the operator during decomposition, disassembly, etc. after use in a heated environment.
- fibers having good fiber quality can be obtained by a normal production method. Furthermore, since the melt for producing the fiber of the present invention has a low viscosity, fine fibers can be formed at a low temperature. During production, the fiber diameter can be reduced by spinning at a high temperature and high speed. The average fiber diameter is usually 2 to 6 ⁇ m, preferably 2 to 4 ⁇ m.
- the thin fiber diameter means that the number of fibers per unit volume of the product increases in addition to being easily dissolved even when entering the living body. Rise.
- a processed product having a high density is also obtained during processing, which increases the heat insulation effect.
- the number of fibers is large, the tensile strength is increased, and there are many advantages that the fiber diameter is small.
- the fiber of this invention since the fiber of this invention has few kinds of essential components, the man-hour of a mixing process reduces and it reduces cost. SiO 2 and CaO are inexpensive, but other components are expensive and expensive. In addition, the fact that there are few kinds of components for adjusting delicate blending amounts reduces the difficulty of production.
- the fiber of the present invention can be produced by preparing a melt containing SiO 2 , CaO, MgO, and Al 2 O 3 and fiberizing the melt.
- a melt containing SiO 2 , CaO, MgO, and Al 2 O 3 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.
- processed products such as molded products and irregular materials can be obtained.
- a molded product such as a bulk, a blanket, a block, a board, a mold, a paper, or a felt manufactured using a solvent such as water can be obtained.
- the amorphous material (mastic, a caster, a coating material, etc.) manufactured using solvents, such as water, is also obtained. These are used as heat insulating materials.
- Example 1 Fibers having the compositions shown in Table 1 were produced.
- the fiber diameter of the obtained fiber was 3.3 ⁇ m, the shape and appearance were good, and there were few flakes that were not fiberized. Furthermore, processed products such as bulk, blanket, block, board, mold, paper, felt, and amorphous material could be produced from this fiber without excessive dissolution of components.
- the fiber diameter was measured by the following method. After observing and photographing the fibers with an electron microscope, 400 or more diameters of the photographed fibers were measured, and the average value of all the measured fibers was defined as the average fiber diameter.
- Comparative Example 1 Fibers having the compositions shown in Table 1 were produced.
- Example 1 The fibers obtained in Example 1 and Comparative Example 1 were measured for biosolubility after heating at 800 ° C. to 1260 ° C. by the following method. Each fiber was placed on a membrane filter, and 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 and 48 hours, and the eluted components were quantified with an ICP emission spectrometer, and the solubility and dissolution rate constant were calculated. The measurement elements were four elements of Si, Al, Ca and Mg, which are main elements.
- the physiological saline composition is as shown in Table 2.
- Example 1 Regarding the fibers obtained in Example 1 and Comparative Example 1, the relationship between temperature and viscosity was examined using a ball pulling-up type viscosity measuring device in an electric furnace capable of raising the temperature to 2500 ° C. The results are shown in FIG. As shown in the figure, compared to Comparative Example 1, Example 1 has a gentle viscosity curve with respect to temperature. From this, the fiber of Example 1 does not need to have a high melting temperature, that is, it can be melted at low energy, and the melt is stretched to become a fiber because the viscosity is low at the same melting temperature. As a result, the fiber diameter can be reduced.
- Example 3 For the fiber obtained in Example 1, the tensile strength of a 25 mm thick blanket having a density of 128 kg / m 3 was measured. The results are shown in Table 4. In the table, the results of the blanket tensile strength described in Patent Document 2 (Patent 318) are compared and shown. As shown in Table 4, the tensile strength of Example 1 is equal to or greater than that of the example described in Patent 318 regardless of the presence or absence of La. In particular, in Patent Document 2 (Patent 318), the effect of La 2 O 3 is that “addition of only 1.3% by weight of La 2 O 3 leads to a considerable improvement in tensile strength indicating a very improved fiber. However, in Example 1 of this time, it was confirmed that even if La 2 O 3 was not added, it had a tensile strength equal to or higher than that of the added product.
- Comparative Examples 2 to 4 in which the amount of alumina is outside the present invention are particularly inferior in heat shrinkage.
- the inorganic fiber of this invention can be used for various uses as a heat insulating material and a substitute for asbestos.
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Abstract
Description
生体溶解性無機繊維は、原料の粘度が高く、極めて高温にしなければ紡糸できなかった。そのため繊維径の細い繊維が得難かった。
また、繊維の水溶性が高いと成形しにくいという問題もあった。
本発明によれば、以下の無機繊維等が提供される。
1.以下の組成を有する無機繊維。
SiO2 71~80重量%
CaO 18~27重量%
MgO 0~3重量%
Al2O3 1.1~3.4重量%
但し、ZrO2、R2O3(R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)はそれぞれ0.1重量%以下であり、アルカリ金属酸化物は各々0.2重量%以下であり、
SiO2、CaO、MgO、Al2O3の合計は99重量%以上である。
2.アルカリ金属酸化物が各々0.1重量%以下である1記載の無機繊維。
3.TiO2、ZnO、B2O3、P2O5がそれぞれ0.1重量%以下である1又は2記載の無機繊維。
4.Al2O3が1.1~1.95重量%である1~3のいずれか記載の無機繊維。
5.Al2O3が2.0~3.4重量%である1~3のいずれか記載の無機繊維。
6.Al2O3が1.3~2.5重量%である1~3のいずれか記載の無機繊維。
7.SiO2が71.25重量%以上である1~6のいずれか記載の無機繊維。
8.以下の組成を有する無機繊維。
SiO2 71~80重量%
CaO 18~27重量%
MgO 0~3重量%
Al2O3 2.0~3.4重量%
但し、ZrO2、R2O3(R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)はそれぞれ0.1重量%以下であり、
SiO2、CaO、MgO、Al2O3の合計は99重量%以上である。
9.アルカリ金属酸化物を各々0.01重量%より多く含む1~8のいずれか記載の無機繊維。
10.SiO2が71~77重量%である1~6及び8~9のいずれか記載の無機繊維。
11.SiO2が71~76重量%である10記載の無機繊維。
12.CaOが20~27重量%である1~11のいずれか記載の無機繊維。
13.CaOが21~26重量%である12記載の無機繊維。
14.平均繊維径が2~6μmである1~13のいずれか記載の無機繊維。
15.平均繊維径が2~4μmである14記載の無機繊維。
16.SiO2、CaO、MgO、Al2O3を含む溶融物を作製し、
前記溶融物を繊維化する1~15のいずれか記載の無機繊維の製造方法。
17.1~15のいずれか記載の無機繊維を用いて得られる加工品
SiO2 71~80重量%
CaO 18~27重量%
MgO 0~3重量%
Al2O3 1.1~3.4重量%
本発明の繊維は、通常、R2O3(R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)を含まない。R2O3は0.1重量%以下又は0.1重量%未満である。
K2Oは含まれても含まれなくてもよく、0.2重量%以下、0.15重量%以下又は0.1重量%以下とすることができる。K2Oは0.01重量%超、0.05重量%以上又は0.08重量%以上含まれていてもよい。
Na2Oは含まれても含まれなくてよく、0.2重量%以下、0.15重量%以下又は0.1重量%以下とすることができる。Na2Oは0.01重量%超、0.05重量%以上又は0.08重量%以上含まれていてもよい。
Fe2O3は0.1~0.3重量%含まれていてもよい。
Fe2O3を含むとき、SiO2、CaO、MgO、Al2O3、Fe2O3の合計は、99.7重量%以上、99.8重量%以上、99.9重量%以上、又は100重量%とすることができる。
CaOが18~27重量%であると生体溶解性に優れ、製品引張強度も高くなる。好ましくは20~27重量%であり、より好ましくは21~26重量%、さらに好ましくは23~26重量%である。
MgOが0~3重量%であると生体溶解性に優れる。MgOが多すぎると加熱後生体溶解性が悪化する恐れがある。好ましくは0~1重量%である。通常0重量%を超えて存在する。
Al2O3の量を1.3~1.95重量%又は1.4~1.7重量%とすることができる。また、Al2O3の量を1.5~3又は2~3重量%とすることができる。Al2O3の量が2.0重量%以上のとき、アルカリ金属酸化物を0.2重量%以上(例えば0.2~1.5重量%)含んでもよい。
表1に示す組成の繊維を製造した。得られた繊維の繊維径は3.3μmであり、形状、外観は良好であり、未繊維化物であるフレークも少なかった。さらにこの繊維からバルク、ブランケット、ブロック、ボード、モールド、ペーパー、フェルト、不定形材料等の加工品が、過度に成分が溶出することなく、製造できた。
尚、繊維径は以下の方法で測定した。
繊維を電子顕微鏡で観察・撮影した後、撮影した繊維について、その径を400本以上計測し、全計測繊維の平均値を平均繊維径とした。
表1に示す組成の繊維を製造した。
実施例1と比較例1で得た繊維について、以下の方法で、未加熱、800℃~1260℃での加熱後における生体溶解性を測定した。
各繊維を、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、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した。また、測定元素は主要元素であるSi、Al、Ca、Mgの4元素とした。尚、生理食塩水配合は表2に示す通りである。
繊維の生体溶解性を評価するには、単純な溶解度では繊維の表面積(≒繊維径)の違いによる影響が出ると考えられるため、繊維径を測定する事で単位表面積・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)に換算して評価した。
加熱温度毎の溶解速度定数を表3に示す。
表3に示すように、比較例1では1000℃以上の加熱により生理食塩水への溶解性が著しく低下するのに対し、実施例1では低下は見られず増加している。これは、繊維の加熱により構成成分から生成される結晶種の差に起因すると考えられる。
実施例1と比較例1で得た繊維について、2500℃まで昇温可能な電気炉において、球引き上げ式の粘度測定器を用いて温度と粘度の関係を調べた。結果を図1に示す。
図に示す通り実施例1は比較例1に比べ、温度に対する粘度カーブが緩やかである。このことから、実施例1の繊維は、熔解温度を高くする必要はなく、即ち、低エネルギーで熔解可能であり、また、同じ熔解温度でも粘性が低い分、融液が引き延ばされ繊維化する工程も速やかに進み、結果として繊維径を細くすることができる。
実施例1で得た繊維について、128kg/m3の密度を有する25mm厚のブランケットの引張強度を測定した。結果を表4に示す。尚、同表には特許文献2(特許318)に記載されているブランケット引張強度の結果を比較して示す。
表4に示す通り、実施例1の引張強度は特許318記載実施例に比べ、Laの無し、有りに拘わらず同等以上の値を示している。特に特許文献2(特許318)ではLa2O3の効果として、「1.3重量%だけのLa2O3の添加が、非常に改善された繊維を示す引張強度における相当な改善につながるということが分かる」と記載されているが、今回の実施例1ではLa2O3を添加しなくても、添加品と同等以上の引張強度を有することが確認できた。
表5に示す組成の繊維を製造し、評価した。
加熱収縮率は、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した。
引張強度は万能試験機により測定した。
生体溶解性は評価例1と同様にして測定した。
上記に本発明の実施形態及び/又は実施例を幾つか詳細に説明したが、当業者は、本発明の新規な教示及び効果から実質的に離れることなく、これら例示である実施形態及び/又は実施例に多くの変更を加えることが容易である。従って、これらの多くの変更は本発明の範囲に含まれる。
この明細書に記載の文献の内容を全てここに援用する。
Claims (17)
- 以下の組成を有する無機繊維。
SiO2 71~80重量%
CaO 18~27重量%
MgO 0~3重量%
Al2O3 1.1~3.4重量%
但し、ZrO2、R2O3(R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)はそれぞれ0.1重量%以下であり、アルカリ金属酸化物は各々0.2重量%以下であり、
SiO2、CaO、MgO、Al2O3の合計は99重量%以上である。 - アルカリ金属酸化物が各々0.1重量%以下である請求項1記載の無機繊維。
- TiO2、ZnO、B2O3、P2O5がそれぞれ0.1重量%以下である請求項1又は2記載の無機繊維。
- Al2O3が1.1~1.95重量%である請求項1~3のいずれか記載の無機繊維。
- Al2O3が2.0~3.4重量%である請求項1~3のいずれか記載の無機繊維。
- Al2O3が1.3~2.5重量%である請求項1~3のいずれか記載の無機繊維。
- SiO2が71.25重量%以上である請求項1~6のいずれか記載の無機繊維。
- 以下の組成を有する無機繊維。
SiO2 71~80重量%
CaO 18~27重量%
MgO 0~3重量%
Al2O3 2.0~3.4重量%
但し、ZrO2、R2O3(R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)はそれぞれ0.1重量%以下であり、
SiO2、CaO、MgO、Al2O3の合計は99重量%以上である。 - アルカリ金属酸化物を各々0.01重量%より多く含む請求項1~8のいずれか記載の無機繊維。
- SiO2が71~77重量%である請求項1~6及び請求項8~9のいずれか記載の無機繊維。
- SiO2が71~76重量%である請求項10記載の無機繊維。
- CaOが20~27重量%である請求項1~11のいずれか記載の無機繊維。
- CaOが21~26重量%である請求項12記載の無機繊維。
- 平均繊維径が2~6μmである請求項1~13のいずれか記載の無機繊維。
- 平均繊維径が2~4μmである請求項14記載の無機繊維。
- SiO2、CaO、MgO、Al2O3を含む溶融物を作製し、
前記溶融物を繊維化する請求項1~15のいずれか記載の無機繊維の製造方法。 - 請求項1~15のいずれか記載の無機繊維を用いて得られる加工品。
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