WO2012132287A1 - 生体溶解性無機繊維の製造方法 - Google Patents
生体溶解性無機繊維の製造方法 Download PDFInfo
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- WO2012132287A1 WO2012132287A1 PCT/JP2012/001787 JP2012001787W WO2012132287A1 WO 2012132287 A1 WO2012132287 A1 WO 2012132287A1 JP 2012001787 W JP2012001787 W JP 2012001787W WO 2012132287 A1 WO2012132287 A1 WO 2012132287A1
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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
- 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
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
- C03B37/01—Manufacture of glass fibres or filaments
- C03B37/04—Manufacture of glass fibres or filaments by using centrifugal force, e.g. spinning through radial orifices; Construction of the spinner cups therefor
- C03B37/05—Manufacture of glass fibres or filaments by using centrifugal force, e.g. spinning through radial orifices; Construction of the spinner cups therefor by projecting molten glass on a rotating body having no radial orifices
- C03B37/055—Manufacture of glass fibres or filaments by using centrifugal force, e.g. spinning through radial orifices; Construction of the spinner cups therefor by projecting molten glass on a rotating body having no radial orifices by projecting onto and spinning off the outer surface of the rotating body
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
- C03B37/01—Manufacture of glass fibres or filaments
- C03B37/04—Manufacture of glass fibres or filaments by using centrifugal force, e.g. spinning through radial orifices; Construction of the spinner cups therefor
- C03B37/05—Manufacture of glass fibres or filaments by using centrifugal force, e.g. spinning through radial orifices; Construction of the spinner cups therefor by projecting molten glass on a rotating body having no radial orifices
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/26—Outlets, e.g. drains, siphons; Overflows, e.g. for supplying the float tank, tweels
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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
- C03C13/00—Fibre or filament compositions
- C03C13/06—Mineral fibres, e.g. slag wool, mineral wool, rock wool
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/18—Formation of filaments, threads, or the like by means of rotating spinnerets
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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
Definitions
- the present invention relates to a method for producing a biosoluble inorganic fiber.
- 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 Documents 3 and 4 describe that an inorganic fiber having an average fiber diameter of 100 to 2000 nm or 3 to 50 ⁇ m is produced by an electrospinning method. Further, Patent Document 5 describes that an inorganic fiber mainly composed of alumina having an average fiber diameter of 4 to 10 ⁇ m is produced by a blowing method in which a raw material melt is made into fibers by applying it to compressed air. .
- Patent Documents 6 to 9 describe the air spinning method in which a raw material melt is supplied to a rotor and the centrifugal force of the rotor and the surroundings of the rotor are ejected.
- Patent Documents 8 and 9 describe that fibers having good physical properties can be obtained by producing rock wool having a SiO 2 content of less than 70% at a high centrifugal acceleration.
- Patent Document 6 describes a method in which the fiber diameter can be controlled by the viscosity of the melt and centrifugal acceleration.
- Patent Document 7 describes the wind speed of the first rotor.
- the biosoluble inorganic fiber contains silica (SiO 2 ) as a main component and includes calcia (CaO), magnesia (MgO), and the like.
- silica SiO 2
- CaO calcia
- MgO magnesia
- the fire resistance is increased when the silica content is high
- fibers having a high silica content have been developed in recent years.
- silica is contained in an amount of 70% by weight or more, the viscosity of the raw material becomes high, so that it is difficult to obtain a fiber having a thin fiber diameter, and the fiber diameter of biosoluble fibers currently on the market is 4.5 ⁇ m or more. It was extremely difficult to stably spin thin fibers of several ⁇ m with few unfibrinated products (shots) at a high temperature of about 2000 ° C.
- An object of the present invention is to provide a biosoluble inorganic material having a stable and thin fiber diameter, even if the fiber is difficult to manufacture or difficult to manufacture because of high viscosity in the conventional manufacturing method, or a fiber that can only be manufactured with a large fiber diameter. It is to provide a method by which fibers can be produced industrially.
- an inorganic raw material containing about 70 wt% or more of silica and about 10 wt% to about 30 wt% of magnesia and calcia combined is heated and melted in a container to obtain a melt having a melt viscosity of about 15 poise or less.
- the production method according to 1 or 2 wherein a melt having a melt viscosity of about 4 poise or less is produced, and the melt is supplied to a rotor rotating at an acceleration of about 115 km / s 2 or more. 4).
- the production method according to 1 or 2 wherein a melt having a melt viscosity of about 7 poise or less is produced, and the melt is supplied to a rotor rotating at an acceleration of about 259 km / s 2 or more. 5.
- the production method according to 1 or 2 wherein the melt viscosity of the melt and the acceleration of the rotor satisfy the following formula.
- a ⁇ 36.81 ⁇ P-11.21 15 ⁇ P (In the formula, P is the melt viscosity (poise) of the melt, and A is the acceleration (km / s 2 ) of the rotor.) 6). 6. The production method according to any one of 1 to 5, wherein the electric power applied per unit raw material is melted at about 0.15 kW / kg to about 0.70 kW / kg. 7. 7. The production method according to 6, wherein the electric power applied per unit raw material is melted at about 0.25 kW / kg to about 0.70 kW / kg. 8). A hole for supplying the melt to the rotor at the bottom of the container; A rod is provided in the container toward the hole, 8.
- 10. The production method according to any one of 1 to 9, wherein a speed at which the melt is supplied to the rotor is about 100 kg / hour to about 1000 kg / hour.
- a speed at which the melt is supplied to the rotor is about 250 kg / hour to about 800 kg / hour.
- a biosoluble inorganic fiber having a small fiber diameter can be produced industrially.
- the object of the present invention is to produce inorganic fibers (silica / alkaline earth metal fibers) containing 70% by weight or more of silica and 10 to 30% by weight of magnesia and calcia combined. Such fibers are known as biosoluble.
- Silica / alkaline earth metal fibers are used in various applications such as heat insulating materials, but it is desirable that the average fiber diameter is as thin as about 5 ⁇ m or less. If the fiber diameter is small, it will easily dissolve even if it enters the living body. Furthermore, the touch is smooth and no tingling sensation occurs. Moreover, that the fiber diameter is thin means that the number of fibers per unit volume of the product is increased, thereby reducing the thermal conductivity and increasing the heat insulation effect. Also during the processing, a processed product having a high density is obtained, which increases the heat insulating effect. Furthermore, when the number of fibers is large, the tensile strength increases. Thus, there are many advantages of a thin fiber diameter.
- the fiber diameter must not be too thin for molding.
- a nanometer level fiber is obtained by an electrospinning method, but such a fiber is not a fiber to be manufactured by the present invention.
- the fiber diameter is 2 ⁇ m or more.
- Blowing and spinning methods are known as fiber manufacturing methods, but silica / alkaline earth metal fibers are often unfibrinated by the blowing method. Therefore, the present invention is manufactured using a spinning method.
- a raw material melt is supplied to a rotating rotor, and the melt is stretched into fibers by centrifugal force of the rotor and air ejected from the periphery of the rotor.
- the spinning method it is necessary to dissolve at an extremely high temperature in order to produce fine fibers containing 70% by weight or more of silica. Accordingly, it is necessary to achieve a high temperature and to allow the melt to flow stably to the rotor without being damaged in the high temperature. If the outflow is not stable, the state in which the melt is in contact with the rotor becomes unstable, and the fiber properties deteriorate.
- the present invention achieves such high-temperature melting and stable outflow by combining a plurality of conditions, and industrially produces fine silica / alkaline earth metal fibers having good fiber quality and an average fiber diameter of about 5 ⁇ m or less. Made possible. In addition, an average fiber diameter can be calculated
- the non-fibrosis product of 45 ⁇ m or more of the obtained fiber is usually 65% or less, for example 55 to 30%.
- the amount of unfibrinated material can also be determined by the method described in the examples.
- FIG. 1 shows an example of an apparatus that can be used in the manufacturing method of the present embodiment.
- silica sand, magnesium oxide, and magnesium carbonate are used in the container 10.
- Melt raw materials such as wollastonite, calcium carbonate, strontium carbonate, kaolin, alumina, etc. to produce a melt with a low viscosity of 15 poise or less, preferably 10 poise or less, 7 poise or less, 5 poise or 4 poise or less To do.
- the lower limit is, for example, 1 poise or more from the viewpoint of ease of implementation.
- the heating temperature is not limited as long as it has a predetermined viscosity, but it is usually about 1600 to 2400 ° C, particularly about 1700 to 2400 ° C. Preferably all the necessary raw materials here are melted.
- the container 10 two or more electrodes 12 are provided and heated by the electrodes to melt the raw material.
- the electrode 12 may be any material that can withstand high temperatures such as molybdenum.
- the container 10 is preferably made of boiler steel plate and has a cooling device.
- the applied power to the electrode 12 is preferably 0.15 to 0.70 kW / kg, more preferably 0.25 to 0.70 kW / kg.
- the container 10 Below the container 10, there is an orifice 14 for allowing the melt to flow out to the rotor 20, and a funnel-shaped hole 16 is formed in the orifice.
- the outflow rate is adjusted by adjusting the diameter and length of the orifice hole. The larger the hole diameter and the shorter the length, the greater the outflow. If the high-temperature melt is kept flowing, the orifice wall is damaged and the diameter of the hole increases. As the hole diameter increases, the amount of outflow increases and becomes unstable. Therefore, in the apparatus shown in FIG. 1, the rod 18 is provided in the container 10 in the vertical direction toward the hole 16.
- the tip of the rod preferably corresponds to the shape of the hole, and in this device the tip is sharp.
- the control rod is preferably lowered so that the supply amount of the melt to the rotor is adjusted to be constant.
- the melt is supplied from the orifice 14 to the rotating rotor 20.
- the supply rate is, for example, 100 to 1000 kg / hour, preferably about 250 to 800 kg / hour.
- Two or more (preferably 2 to 4) rotors are used, and the opposing rotors rotate inward (arrow A) clockwise and counterclockwise.
- the melt is supplied to the peripheral surface of one rotor.
- the molten liquid travels around the peripheral surfaces of the plurality of rotors.
- the acceleration of the rotor is 70 km / s 2 or more.
- the acceleration of all the rotors is 70 km / s 2 or more.
- the acceleration is preferably 100 km / s 2 or more, more preferably 150 km / s 2 or more, and further preferably 250 km / s 2 or more.
- the upper limit is, for example, 550 km / s 2 or less from the viewpoint of ease of implementation.
- the melt viscosity is 4 poises or less, and the acceleration is 115 km / s 2 or more. Further, the melt viscosity is set to 7 poise or less, and the acceleration is set to 259 km / s 2 or more.
- D ⁇ 1.16 ⁇ 10 ⁇ 2 ⁇ A + 4.27 ⁇ 10 ⁇ 1 ⁇ P + 4.87 (In the formula, D is the fiber diameter ( ⁇ m), P is the melt viscosity (poise) of the melt, and A is the acceleration (km / s 2 ) of the rotor.)
- the melt viscosity P (poise) of the melt is P> 0, preferably P ⁇ 0.5, more preferably P ⁇ 1.
- Stripping air is blown around the rotor 20 toward the collector 30 (arrow B). It is preferable to provide a stripping air blowing port in the vicinity of the rotor.
- the distance from the stripping air blowing port to the periphery of the rotor is preferably 0 to 300 mm. It can be provided on the rotor or can be provided away from the rotor.
- the fibers blown off by the stripping air are collected in the collector 30 to obtain an aggregate of inorganic fibers.
- the silica / alkaline earth metal fiber produced by the method of the present invention contains 70% by weight or more of silica and 10 to 30% by weight of magnesia and calcia.
- the silica content is 70% by weight or more, the heat resistance is excellent.
- the combined amount of magnesia and calcia is 10 to 30% by weight, the biosolubility is excellent.
- the amount of silica is preferably 70 to 80% by weight, more preferably 71 to 79% by weight.
- the total amount of magnesia and calcia is preferably 15 to 28% by weight, more preferably 19 to 28% by weight.
- Al 2 O 3 (for example, 5 wt% or less, 1 to 4 wt% or 1 to 2 wt%), K 2 O, Na 2 O, Fe 2 O 3 , ZrO 2 , P 2 O 4 , B 2 O 3 , La 2 O 3 and the like can be included.
- the total of SiO 2 , CaO, MgO, and Al 2 O 3 may be greater than 95 wt%, greater than 97 wt%, or greater than 98 wt%.
- Such fibers can be broadly classified into Mg silicate fibers containing a lot of MgO and Ca silicate fibers containing a lot of CaO.
- the following composition can be illustrated as Mg silicate fiber.
- SiO 2 70 to 82% by weight preferably 70 to 80% by weight, more preferably 71 to 79% by weight
- CaO 1-9% by weight preferably 2-8% by weight
- MgO 10-29% by weight preferably 10-25% by weight
- Al 2 O 3 less than 3% by weight (preferably less than 2% by weight)
- Other oxides less than 2% by weight (preferably less than 1% by weight)
- Ca silicate fiber Such fibers are preferred from the viewpoints of heat resistance and biosolubility.
- Ca silicate fibers tend to have a lower melt viscosity at a lower temperature than Mg silicate fibers, and the fiber diameter can be more easily reduced.
- SiO 2 66-82 wt% (for example, 68-82 wt%, 70-82 wt%, 70-80 wt%, 71-80 wt%, or 71.25-76 wt%)
- CaO 10-34% by weight (for example, it can be 18-30% by weight, 18-29% by weight, 20-27% by weight or 21-26% by weight)
- MgO 3 wt% or less eg, 1 wt% or less
- Al 2 O 3 5 wt% or less for example, 3.4 wt% or less or 3.0 wt% or less.
- the total of SiO 2 , CaO, MgO and Al 2 O 3 may be more than 98 wt% or more than 99 wt%.
- the biosoluble inorganic fiber includes alkali metal oxides (K 2 O, Na 2 O, Li 2 O, etc.), Sc, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb as other components. , Dy, Ho, Er, Tm, Yb, Lu, Y, or a mixture thereof, Fe 2 O 3 , ZrO 2 , TiO 2 , P 2 O 5 , B 2 O 3 , MnO, One or more of ZnO, SrO, BaO, Cr 2 O 3 and the like may or may not be included. Other oxides may be 1.0 wt% or less, 0.2 wt% or less, or 0.1 wt% or less, respectively.
- the alkali metal oxide may contain 1.0% by weight or less, 0.2% by weight or less, or 0.1% by weight or less of each oxide.
- the total of the alkali metal oxides may be 1.0% by weight or less, 0.2% by weight or less, or 0.1% by weight or less.
- the above-mentioned fibers have excellent biosolubility by having the above composition, and especially the biosolubility increases after heating.
- Experimental example 1 The raw materials of fiber A and fiber B having the composition shown in Table 1 were melted by applying an electric power of 0.15 kW / kg to the electrode in a container and heated to 1700-2400 ° C., and having a melt viscosity of 1-15 poise. A melt was produced.
- FIG. 2 shows the relationship between the melt viscosity of the fibers A and B and the temperature.
- melts were fed from the orifice of the vessel to a rotor rotating at an acceleration of 74, 115, 259 km / s 2 at about 300-600 kg / hr.
- the control rod was adjusted so that the supply amount was within a certain range. Fibers were produced while blowing air around the rotor. The relationship between the melt viscosity of the fibers A and B obtained and the average fiber diameter is shown in FIG.
- the measurement method of the characteristics in the experimental example is as follows. (1) Average fiber diameter After observing and photographing the fiber with an electron microscope, 400 or more diameters of the photographed fiber were measured, and the average value of all the measured fibers was defined as the average fiber diameter.
- Fibers C and D having the composition (wt%) shown in Table 4 were produced by the following method.
- the raw material was heated and melted in a container to produce a melt having a melt viscosity of 5 to 6 poise, and this melt was supplied to a rotor rotating at an acceleration of 259 km / s 2 .
- the melt was drawn into fibers by centrifugal force generated by the rotation of the rotor. Air was blown around the rotor, fiberized fibers were blown, and the fibers were collected.
- the average fiber diameter was measured by the method described in Example 1, and the tensile strength was 25 mm thick blanket having a density of 128 kg / m 3 from the fiber. It was measured by.
- the results are shown in Table 4.
- the obtained fiber had good appearance and shape, and few unfibrinated products. It also had good tensile strength.
- the inorganic fiber obtained by the method of the present invention can be used in various applications as a heat insulating material or as a substitute for asbestos.
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Abstract
Description
本発明によれば、以下の製造方法が提供される。
1.シリカを約70重量%以上と、マグネシアとカルシアを合わせて約10重量%~約30重量%含む無機原料を、容器の中で加熱して溶融させて、溶融粘度約15ポアズ以下の溶融液を製造し、
前記溶融液を、約70km/s2以上の加速度で回転するロータに供給し、
前記ロータの回転による遠心力により、前記溶融液を引き延ばして繊維化し、
前記ロータの周囲に空気を吹き付け、前記繊維化した繊維を飛ばし、
前記繊維を集めて平均繊維径約5μm以下の繊維を製造する、無機繊維の製造方法。
2.前記加速度が、約100km/s2以上である1記載の製造方法。
3.溶融粘度約4ポアズ以下の溶融液を製造し、前記溶融液を、約115km/s2以上の加速度で回転するロータに供給する1又は2記載の製造方法。
4.溶融粘度約7ポアズ以下の溶融液を製造し、前記溶融液を、約259km/s2以上の加速度で回転するロータに供給する1又は2記載の製造方法。
5.溶融液の溶融粘度と、ロータの加速度が下記式を満たす1又は2記載の製造方法。
A≧36.81×P-11.21
15≧P
(式中、Pは溶融液の溶融粘度(ポアズ)であり、Aはロータの加速度(km/s2)である。)
6.単位原料当たりに印加する電力を約0.15kW/kg~約0.70kW/kgとして熔融させる1~5のいずれか記載の製造方法。
7.単位原料当たりに印加する電力を約0.25kW/kg~約0.70kW/kgとして熔融させる6記載の製造方法。
8.前記容器の底に、前記溶融液をロータに供給するための孔と、
前記容器の中に、前記孔に向かって、ロッドを設け、
前記孔の径が広がると前記ロッドを孔に近づけて、前記ロータへの溶融液の供給量を調整する1~7のいずれかに記載の製造方法。
9.前記加熱温度が、約1600℃~約2500℃である1~8のいずれかに記載の製造方法。
10.前記ロータへ溶融液を供給する速度が約100kg/時~約1000kg/時である1~9のいずれかに記載の製造方法。
11.前記ロータへ溶融液を供給する速度が約250kg/時~約800kg/時である10に記載の製造方法。
12.前記繊維の平均繊維径が約2μm~約4.4μmである1~11のいずれかに記載の製造方法。
13.前記繊維の約45μm以上の未繊維化物が約65重量%以下である1~12のいずれかに記載の製造方法。
14.前記繊維が以下の組成1又は組成2を有する1~13のいずれかに記載の製造方法。
繊維径が細いと、生体内に入っても容易に溶解しやすい。さらに、手触りが滑らかであり、チクチク感が生じない。また、繊維径が細いことは、製品単位体積当たりの繊維本数が増えることを意味しており、これにより熱伝導率が低くなり断熱効果が高まる。加工の際も、密度の高い加工品が得られ、このことにより断熱効果が高まる。さらに、繊維本数が多いと引張強度も大きくなる。このように、繊維径が細いことの利点は多い。
図1に本実施形態の製造方法に用いることのできる装置の一例を示す。
まず、容器10の中で、珪砂、酸化マグネシウム、炭酸マグネシウム。ワラストナイト、炭酸カルシウム、炭酸ストロンチウム、カオリン、アルミナ等の原料を溶融し、溶融粘度15ポアズ以下、好ましくは10ポアズ以下、7ポアズ以下、5ポアズ、4ポアズ以下と低い粘度の溶融液を製造する。下限は、実現容易性の観点から、例えば、1ポアズ以上である。加熱温度は所定の粘度になれば限定されないが、通常1600~2400℃、特に1700~2400℃程度である。好ましくはここで必要な原料の全てを溶融する。
ロータは2以上(好ましくは2~4)用い、対向するロータは互いに内向き(矢印A)に時計回り、反時計周りに回転する。溶融液を1つのロータの周面に供給する。溶融液は複数のロータの周面を伝わっていく。
例えば、溶融粘度を4ポアズ以下として、加速度を115km/s2以上とする。また、溶融粘度を7ポアズ以下として、加速度を259km/s2以上とする。
D=-1.16×10-2×A+4.27×10-1×P+4.87
(式中、Dは繊維径(μm)であり、Pは溶融液の溶融粘度(ポアズ)であり、Aはロータの加速度(km/s2)である。)
A≧36.81×P-11.21
15≧P
(式中、Pは溶融液の溶融粘度(ポアズ)であり、Aはロータの加速度(km/s2)である。)
シリカの量は、好ましくは70~80重量%、より好ましくは71~79重量%である。
マグネシアとカルシアを合わせた量は、好ましくは15~28重量%、より好ましくは19~28重量%である。
SiO2 70~82重量%(好ましくは70~80重量%、より好ましくは71~79重量%)
CaO 1~9重量%(好ましくは2~8重量%)
MgO 10~29重量%(好ましくは10~25重量%)
Al2O3 3重量%未満(好ましくは2重量%未満)
他の酸化物 2重量%未満(好ましくは1重量%未満)
SiO2 66~82重量%(例えば、68~82重量%、70~82重量%、70~80重量%、71~80重量%又は71.25~76重量%とできる)
CaO 10~34重量%(例えば、18~30重量%、18~29重量%、20~27重量%又は21~26重量%とできる)
MgO 3重量%以下(例えば、1重量%以下とできる)
Al2O3 5重量%以下(例えば3.4重量%以下又は3.0重量%以下とできる。また、0.1重量%以上、0.5重量%以上、1.1重量%以上又は2.0重量%以上とできる)
他の酸化物 2重量%未満
表1に示す組成の繊維Aと繊維Bの原料を、容器の中で電極に電力を0.15kW/kg印加して、1700~2400℃に加熱して溶融させ、溶融粘度1~15ポアズの溶融液を製造した。図2に、繊維A,Bの溶融粘度と温度の関係を示す。
(1)平均繊維径
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。
繊維を45μmの目開きを有する篩で篩下部より吸引しながら繊維を擦り、篩上に残った粒子を未繊維化物とした。
球引き上げ式の粘度測定器を用いて測定した。
実験例1と同様にして、溶融粘度が5ポアズで、加速度が259km/s2で繊維Aを製造した。本実験例では、溶融液をロータに供給する際、コントロールロッドを用いたときと、用いなかったときの溶融液の流出量の経時変化を測定した。ロッドはオリフィスの孔が広がるのに応じて高さを下げた。結果を図4と表2に示す。図4にはロッドの高さも合わせて示す。ロッドを用いることにより、流出量のばらつきを抑えることができ、繊維径が細くなることが分かる。
実験例1と同様にして、溶融粘度が5ポアズで、加速度が259km/s2で繊維Aを製造した。本実験例では、容器への印加電力を変えて、溶融液の流出温度と粘度を測定した。結果を表3に示す。
表4に示す組成(wt%)の繊維C,Dを以下の方法で製造した。
原料を容器の中で加熱して溶融し、溶融粘度5~6ポアズの溶融液を製造し、この溶融液を、259km/s2の加速度で回転するロータに供給した。ロータの回転による遠心力により、溶融液を引き延ばして繊維化した。ロータの周囲に空気を吹き付け、繊維化した繊維を飛ばし、繊維を集めた。
得られた繊維について、平均繊維径を実施例1に記載の方法で測定し、引張強度は、繊維から128kg/m3の密度を有する25mm厚のブランケットを作製し、その引張強度を万能試験機により測定した。結果を表4に示す。得られた繊維は、外観、形状が良好で、未繊維化物が少なかった。また良好な引張強度を有していた。
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 (14)
- シリカを70重量%以上と、マグネシアとカルシアを合わせて10~30重量%含む無機原料を、容器の中で加熱して溶融させて、溶融粘度15ポアズ以下の溶融液を製造し、
前記溶融液を、70km/s2以上の加速度で回転するロータに供給し、
前記ロータの回転による遠心力により、前記溶融液を引き延ばして繊維化し、
前記ロータの周囲に空気を吹き付け、前記繊維化した繊維を飛ばし、
前記繊維を集めて平均繊維径5μm以下の繊維を製造する、無機繊維の製造方法。 - 前記加速度が、100km/s2以上である請求項1記載の製造方法。
- 溶融粘度4ポアズ以下の溶融液を製造し、前記溶融液を、115km/s2以上の加速度で回転するロータに供給する請求項1又は2記載の製造方法。
- 溶融粘度7ポアズ以下の溶融液を製造し、前記溶融液を、259km/s2以上の加速度で回転するロータに供給する請求項1又は2記載の製造方法。
- 溶融液の溶融粘度と、ロータの加速度が下記式を満たす請求項1又は2記載の製造方法。
A≧36.81×P-11.21
15≧P
(式中、Pは溶融液の溶融粘度(ポアズ)であり、Aはロータの加速度(km/s2)である。) - 単位原料当たりに印加する電力を0.15~0.70kW/kgとして熔融させる請求項1~5のいずれか記載の製造方法。
- 単位原料当たりに印加する電力を0.25~0.70kW/kgとして熔融させる請求項6記載の製造方法。
- 前記容器の底に、前記溶融液をロータに供給するための孔と、
前記容器の中に、前記孔に向かって、ロッドを設け、
前記孔の径が広がると前記ロッドを孔に近づけて、前記ロータへの溶融液の供給量を調整する請求項1~7のいずれかに記載の製造方法。 - 前記加熱温度が、1600~2500℃である請求項1~8のいずれかに記載の製造方法。
- 前記ロータへ溶融液を供給する速度が100~1000kg/時である請求項1~9のいずれかに記載の製造方法。
- 前記ロータへ溶融液を供給する速度が250~800kg/時である請求項10に記載の製造方法。
- 前記繊維の平均繊維径が2~4.4μmである請求項1~11のいずれかに記載の製造方法。
- 前記繊維の45μm以上の未繊維化物が65重量%以下である請求項1~12のいずれかに記載の製造方法。
- 前記繊維が以下の組成1又は組成2を有する請求項1~13のいずれかに記載の製造方法。
[組成1]
SiO2 70~82重量%
CaO 1~9重量%
MgO 10~29重量%
Al2O3 3重量%未満
[組成2]
SiO2 70~82重量%
CaO 10~29重量%
MgO 1重量%以下
Al2O3 3重量%未満
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AR085745A1 (es) | 2013-10-23 |
BR112013025011A2 (pt) | 2017-01-17 |
AU2012235435A1 (en) | 2013-06-20 |
CN103476977A (zh) | 2013-12-25 |
KR101503203B1 (ko) | 2015-03-16 |
US20120247156A1 (en) | 2012-10-04 |
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AU2012235435B2 (en) | 2015-04-30 |
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