KR0181331B1 - Spinning nozzle and manufacturing method of fiber of metal compound using same - Google Patents

Abstract

The present invention relates to a spinning nozzle for dry spinning a spinning liquid containing a metal compound and an organic polymer compound by blowing. In this spinning nozzle, the air nozzle 6 has projections of rectangular-prism shaped slits formed by opposing inner surfaces extending parallel to each other, while these projections have a pair of cover plates 1, 1. It is formed at the front of and each of the protrusions has a blade edge portion at its free time. The spinning liquid supply nozzle consists of a plurality of linear conduits and is arranged in the air nozzle 6 in such a way that the nozzles are parallel to the parallel surfaces of the cover plate and protrude from the edges of the parallel surfaces. Air is introduced through the gas inlet 5 and sent as an air flow from the air nozzle 6, and the flow of the spinning liquid extruded from the spinning liquid supply nozzle forms a parallel flow. Also, the air flow parallel to the spinning liquid flow is adjusted sufficiently to be in contact with the spinning liquid. Thus, the amount of air used can be significantly reduced and fibers with good quality can be produced.

Description

Spinning nozzle and manufacturing method of fiber of metal compound using same

1 shows an embodiment of a spinning nozzle according to the invention.

FIG. 2 is a view showing the lower cover plate and the side plate which are structural elements of the spinning nozzle shown in FIG.

FIG. 3 shows the spinning solution supply mount used for the spinning nozzle shown in FIG.

4 is a side view of the spinning solution supply mount as viewed from the direction B in FIG.

5 is a cross-sectional view taken along the line D-D of FIG.

6 is a view showing another embodiment of the spinning nozzle according to the present invention.

FIG. 7 is a side view of the spinning nozzle viewed from the direction A in FIG. 1.

The present invention relates to a spinning nozzle. More particularly, the present invention relates to a spinning nozzle for dry spinning a spinning liquid containing a metal compound and an organic polymer compound by a blowing method.

A method of dry spinning a spinning solution containing a metal compound and an organic polymer compound is known from, for example, Japanese Patent Publication No. 36726/1980 or Japanese Patent Publication No. 289131/1986.

This method is generally called the precursor fiber molding method. The precursor fiber produced by the molding method is then calcined at a temperature of 500 to 1300 ° C., whereby final products such as alumina fibers, ceramic fibers, and the like are prepared.

In the case of dry spinning the spinning liquid by blowing, the structure of the spinning nozzle is important.

There is no proposal regarding the structure of the spinneret in the conventionally proposed precursor fiber forming method. Even in the above-mentioned publications, there is only a description that the fiber is extruded through the slit or orifice, and there is no specific description regarding the structure of the spinning nozzle.

SUMMARY OF THE INVENTION An object of the present invention is to eliminate various problems in the prior art of dry spinning spinning liquids by using a blowing method, and to improve the excessive energy cost (i.e. the amount of air used), which is a problem in the prior art while having excellent quality. To provide a spinning nozzle of a specific structure that can be produced.

According to the present invention, there is provided a spinning nozzle for dry spinning a spinning solution containing a metal compound and an organic polymer compound by a blowing method, wherein the spinning nozzle comprises two vertically arranged cover plates each having a blade edge, such as A rectangular-prismatic slit formed between two cover plates, and a plurality of spinneret feed nozzles, wherein the feed nozzles are each formed as linear conduits and these nozzles extend in parallel with the opposing surfaces of the slit and out of the space of the slit. And positioned in the slit to protrude.

In addition, according to the present invention there is provided a method for producing fibers of a metal compound by use of the spinning nozzle described above.

Preferred embodiments of the spinning nozzle according to the present invention will be described in detail with reference to the drawings.

1 is a view showing an embodiment of the spinning nozzle of the present invention. The spinning nozzle is mainly composed of a cover plate 1, a spinning liquid supply mount 2, a spinning liquid supply nozzle 3, and a side plate 4. FIG. 1 shows the cover plate located on the left side of the spinning nozzle in the form of cutting the spinning nozzle in a plate perpendicular to the transverse direction of the cover plate 1.

The cover plate 1 is arranged to be vertically stacked by sandwiching the spinning solution supply mount 2 therebetween. The gas chamber 5 'is formed in each cover plate 1. A plurality of air nozzles 6 are located at the front of the cover plates arranged vertically. The gas inlet 5 is formed in each of the upper part of the upper cover plate and the lower part of the lower cover plate so that gas can be introduced into each gas chamber 5 '.

Each gas chamber 5 'has a cylindrical space formed in the transverse direction of each cover plate 1, a horizontal space formed along the horizontal axis of the cylindrical space, a vertical space formed on the side of the horizontal space and an open side of the vertical space. An inclined space formed, wherein the inclined surface of the spinning solution supply mount 2 cooperates to form the inclined space. The cross-sectional area of the horizontal space is preferably narrower than the cross-sectional area of the vertical space so that the gas is uniformly supplied along the transverse path of the gas chamber 5 '. In addition, it is preferable that the cross-sectional inclination space is gradually reduced in the direction of the gas flow. Moreover, it is preferable to form a plurality of gas inlets 5 in the transverse direction of the gas chamber 5 '.

The air nozzle 6 is a rectangular-prism slit formed by two vertically arranged cover plates each having a blade edge 7 (this is the transverse dimension l in FIG. 1, the axial dimension t). ) And the dimension (c) in the thickness direction). The dimension (c) of the thickness of the slit and the distance (t) of the protrusion of the blade edge are respectively determined according to the conditions for the spinning operation.

The spinning solution supply mount 2 is defined by a rectangular-prism-shaped portion and a triangle-sloped portion formed along the rectangular-prism-shaped portion having the same dimensions as the transverse direction of the cover plate 1. The spinning solution path 8 is formed in the spinning solution supply mount 2 so that the spinning solution path has both open ends extending in the transverse direction of the feed mount. One opening is at the distal surface of the rectangular-prismatic portion and the other opening is near the pyramidal portion of the inclined portion.

The spinning liquid supply mount 2 is arranged so that the rectangular-prism-shaped part of the supply mount is arranged between the vertically nested cover plates 1,1 and the opposite side of the inner space of the cover plate 1,1 and the horizontal space. To be joined to the junction formed in the Each junction of the cover plate 1 is coplanar with the end of the spinneret path formed on the distal surface of the rectangular-prism-shaped part of the spinneret feed mount 2. Accordingly, the spinning solution path 9 having an opening that is open to the rear of the spinning solution supply mount 2, while having a width equal to the width of the spinning solution path formed in the spinning solution supply mount 2, has a top and bottom cover. It is formed between the plates (1, 1). The edge portion contrasted to the rear of the cover plates 1 and 1 is chamfered so that the opening of the spinning solution path 9 is spread outward.

The opposing surfaces of the cover plates 1, 1 forming the air nozzle 6 have the same height as described above, so that the surfaces are coplanar with each other. In addition, the opposing surfaces are maintained in a parallel relationship by the junction of the cover plate 1 and the right angle of the rectangular-prism-shaped portion of the spinning solution supply mount 2 (which is joined to the junction of the cover plate).

The spinning solution supply nozzle 3 consists of a number of linear conduits, one end of which is fixed to the triangular pyramid of the spinning solution supply mount 2 so as to coincide with the direction of the top of the supply mount 2. . In addition, the spinning liquid supply nozzle was arranged at the center of the rectangular-prism slit. Moreover, the feed nozzles are arranged parallel to the opposing surface of the rectangular-prismatic slit and protrude from the slit. The inner diameter d, the pitch p, and the length s of each of the projections of the spinning liquid supply nozzle 3 are determined in accordance with the conditions for the spinning operation.

The side plate 4 is fixed to each side surface of the cover plates 1 and 1 arranged vertically.

In the spinning nozzle according to the invention, the air flow sent out from the air nozzle 6 and the spinning liquid flow extruded from the spinning liquid supply nozzle 3 form a parallel flow. In addition, the airflow flowing in parallel with the spinning liquid flow is sufficiently adjusted to be in contact with the spinning liquid stream. Since the outlet of the air nozzle 6 is a blade edge-type free edge, it is possible to prevent the generation of vortex due to the air flow sent out.

Therefore, according to the spinning nozzle of the present invention, the spinning liquid extruded from the spinning liquid supply nozzle 3 is sufficiently stretched without causing a dispersed state (mist), so that bonding of fibers does not occur. Thus, fibers having good quality can be obtained.

In the spinning nozzle of the present invention, the spinning liquid supply nozzles 3 can be arranged in the air nozzle 6 in close proximity to each other. Therefore, the air flow from the air nozzle 6 can be utilized sufficiently. As a result, the amount used can be significantly reduced. In addition, since the air flow forms a slit shape, the deceleration of the gas velocity can be prevented and the stretching effect can be achieved for a long time. Therefore, the air flow sent out from the air nozzle 6 can reduce the initial speed. From the above point of view, it is possible to achieve a reduction in the amount of air used. In addition, since the air nozzle 6 has a blade edge-shaped free edge, it is possible to effectively suck air from the surrounding space by air flow from the air nozzle 6, so that a sufficient amount of air necessary for subsequent drying steps can be obtained. have.

In the spinning nozzle having the above structure, the dimension of each component can be determined as needed. For example, the liquid amount per single spinning liquid supply nozzle 3 is 1 to 120 ml / h, preferably 5 to 50 ml / h, and the gas velocity at the slit portion of the air nozzle 6 is 10 to 200 m / s, Preferably it is 20-100m / s and typical dimensional relationship is as follows.

(1) the inner diameter d of the spinning liquid supply nozzle 3

d = 0.1 to 0.5 mm

(2) the projection length (s) of the spinning liquid supply nozzle (3)

s = 10d to 100d

(3) the pitch p of the spinning liquid supply nozzle 3

p = 3d to 10d

(4) clearance of the slit part of the air nozzle (c), ie the length in the thickness direction of the rectangular-prism-shaped slit

c = 3d to 20d

(5) The length t of the projections of the parallel surfaces of the air nozzle 6, ie the length in the transverse direction of the rectangular-prism-shaped slit.

t = 2c to 80c

FIG. 2 is a view of the spinning nozzle shown in FIG. 1 showing only the lower cover plate and the side plate with the upper cover plate 1 and the spinning solution supply mount 2 removed. 2, the fact that the spinning liquid can be uniformly supplied to each of the spinning liquid supply nozzles 3, and that the spinning liquid path 9 is smoothed toward the spinning liquid supply mount 2 without causing a flow stagnation. It shows that it has an expanded flared portion 9 '.

3 is a view for showing the spinning solution supply mount 2 to which the spinning solution supply nozzle 3 is attached.

4 is a side view of the spinning solution supply conduit 2 viewed in the direction B in FIG. 3. The spinning solution supply nozzle 3 inserts each end thereof into the fixing part 3 'of the supply mount 2 and fixes it to the spinning solution supply mount 2. The spinning solution path 8 is formed to penetrate the central portion of the spinning solution supply mount 2.

5 is a cross-sectional view of the spinning solution supply mount 2 taken along the line D-D in FIG. In FIG. 5, the end 2 'can be formed in the spinneret supply mount without extending the spinneret path 8 to the end to maintain the strength of the spinneret feed mount 2 and It is understood that leakage of the spinning liquid from the end in the transverse direction of 2) can be prevented.

6 shows another embodiment of the spinneret according to the invention. This aspect is intended to allow the enclosed ambient air to be entrained in the surrounding space without causing any disturbance in accordance with the air flow blown from the air nozzle 6. For this purpose, the cover plate 1 and the side plate 4 are each formed to have an inclined portion so as to comply with the accompanying air flow. In addition, the gas inlet 5 is formed behind the spinning nozzle.

FIG. 7 is a schematic of the radial nozzle projected in the A direction in FIG. The gas chamber 5 'will be described in detail with reference to FIG. The gas chamber 5 'has a cylindrical space 5'-1 formed in each transverse direction of the cover plate 1, and a horizontal space 5'- formed on one side along the central axis of the cylindrical space 5'-1. 2) associated with the inclined portion of the spinning liquid supply mount 2 along the open side wall of the vertical space 5'-3 and the vertical space 5'-3 formed on one side of the horizontal space 5'-2. And inclined spaces 5'-4 formed. The inclined space 5'-4 has a path, in which the cross-sectional area of the path is gradually reduced in the direction of gas flow to adjust the gas discharged through the air nozzle 6 and blow the gas in the transverse direction of the nozzle. Can be prevented.

The spinning nozzle of the present invention is used for dry spinning the spinning liquid using a conventional blowing method. The preparation of the spinning solution, the collection of the spun fibers and the burning of the collected fibers can be carried out as desired according to known techniques.

The spinning solution to be formed into fibers by use of the spinning nozzle of the present invention contains a metal compound and an organic polymer compound capable of forming fibers of an inorganic oxide. As the metal compound, a compound capable of forming an aqueous solution or a colloidal solution can be used. Such compounds include hydrochloric acid of metals such as aluminum, zirconium, silicon, magnesium, thorium, yttrium, calcium, chromium and the like, inorganic acid salts such as sulfuric acid and nitric acid, or organic acid salts and hydroxides such as acetic acid. More particularly, there are aluminum oxychloride, basic aluminum acetate, zirconium oxychloride, basic zirconium acetate and the like. These compounds may be used alone or in combination.

Organic polymer compounds include polyvinyl alcohol, polyethylene glycol, polyethylene oxide, polyacrylamide, starch, acetic acid-modified starch, hydroxyethyl starch, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose and the like.

Spinning solutions can be prepared depending on the nature of the material and the subject of the fiber to be produced. For example, when producing aluminum fibers, silicon compounds such as silica gel, tetraethyl silicate, water-soluble siloxane derivatives, etc. are added to an aluminum oxychloride solution, an organic polymer compound such as polyvinyl alcohol is added to the mixture, and the resulting product is condensed. To have a predetermined solids content.

The silicon compound and the organic polymer compound can be added during or after condensation. In the production of alumina fibers, the ratio of the aluminum material to the silicon material in the original spinning solution is in the range of 65 to 98% by weight, especially 70 to 98% by weight, based on the total amount, calculated as Al ₂ O ₃ and SiO ₂ . It is preferable.

Spinning liquids are generally used to make those having a viscosity in the range of 1 to 1000 poise suitable for spinning. Upon spinning, sufficiently drawn fibers are formed from the spinning solution under conditions that inhibit evaporation of water and decomposition of the spinning solution, and then rapidly dry the fibers. In other words, it is preferable to change from the state of suppressing the evaporation of water to the state of accelerating the evaporation of water while supplying the fiber formed from the spinning liquid to the fiber dust collector.

If the ambient temperature is too high while forming a sufficiently drawn fiber from the spinning solution, it is difficult to obtain a fully drawn fiber by rapid evaporation of water. In addition, the fibers thus formed are defective and the fibers of the inorganic oxide finally produced are broken.

On the other hand, when manufacturing fibers from the spinning solution under low temperature or high wet conditions to suppress evaporation of water, the same atmospheric conditions are maintained even after the formation of the fibers, so that adhesion between the fibers occurs or liquid drops due to elasticity recovery. To facilitate shots. Although this phenomenon occurs when the fiber floats in the air flow, it is also likely to occur when the fiber is collected on the fiber dust collector. Therefore, it is desirable to determine that the temperature of the atmosphere at which the contact between the spinning liquid and the air flow is initiated is 1-20 ° C, the temperature of the air flow near the fiber dust collector is 25-100 ° C, and the relative humidity is 30% or less. . Fiber collected by the fiber dust collector is calcined at 500 ° C or more, preferably in the range of 700 to 1400 ° C. If the calcination temperature is below 500 ° C, only low strength debris fibers are obtained. On the other hand, when the calcination temperature exceeds 1400 ° C., crystal growth appears on the fiber, reducing the strength of the fiber. If necessary, the fiber may be needled or other treatment may be performed before calcination.

EXAMPLE

In the following, the invention will be described in more detail with reference to Examples, but there is no intention to limit the invention to these Examples.

In an embodiment, the shot content is a value obtained by pressing and pulverizing the formed fiber and then sorting the pulverized fiber using a sieve having a 325 mesh size to measure the particles remaining on the sieve. Bulk tensile strength is the value obtained by compressing the fibers to have a density of 0.1 g / cm ³ and pulling them with a span of 40 mm.

Example 1

279 g of 20 wt% silica gel solution and 315 g of 5 wt% polyvinyl alcohol aqueous solution are added to 1 L of an aqueous aluminum oxychloride solution (aluminum content: 75 g / l and AL / CL (atomic ratio) = 1.8) and then mixed. The mixture is condensed at 50 ° C. under reduced pressure to prepare a spinning solution having a viscosity of 40 poise and 30% by weight of alumina / silica.

The spinning solution is spun by a blowing method using the spinning nozzle shown in FIG. The fiber dust collector is fixed at a position about 4 m away from the spinning nozzle and then the formed fibers are collected on the screen of the fiber dust collector. When dust is collected, the air flow near the fiber precipitator is adjusted by introducing a dry 90 ° C. hot air and a parallel air flow parallel to the high speed air flow to achieve a temperature of 35 ° C. and a relative humidity of 30%. Have it.

[Dimension of Spinning Nozzle Used]

(1) Internal diameter d of the spinning liquid supply nozzle 3: 0.3 mm

(2) The length (s) of the protrusion of the spinning liquid supply nozzle 3: 10.0 mm

(3) Pitch (p) of spinning liquid supply nozzle (3): 2.0 mm

(4) Number of spinning liquid supply nozzles (3): 50

(5) Slit gap of air nozzle 6 (c): 3.7mm

(6) Length of rectangular to prism type slit in short axis direction (t): 20.0mm

(7) Length of rectangular-prism type slit in transverse direction (ℓ): 120mm

[Radiation condition]

(1) Amount of solution per single spinning liquid supply nozzle (3): 10 ml / h

(2) Speed of air at the slit of the air nozzle (6): 43 m / s

[Pressure: 2kg / cm ² , temperature: 18 ° C, relative humidity: 40%]

The collected fibers were calcined at 1260 ° C. for 1 hour to obtain alumina fibers having the following physical properties.

Diameter of the fiber: 4.2μm

Shot content: 4% by weight

Bulk Tensile Strength: 1.0kg / cm ²

Comparative Example 1

The spinning nozzle shown in FIG. 1 was modified to carry out alumina fibers except that each free side of the spinning liquid supply nozzle 3 did not protrude from the rectangular-prism-shaped slit formed between the two cover plates 1,1. It prepared in the same manner as in Example 1.

It was found that the spinning solution was not sucked smoothly into the air stream and could not easily be stretched into a fibrous form in a mist form at the free side of the nozzle 3. In addition, the other content of the obtained alumina fiber is considered the numerical value of about 10-30 weight%, and the numerical value fluctuates. Moreover, the bulk tensile strength was as low as 0.4-0.6 kg / cm ² .

Example 2

Alumina fibers were prepared using the spinning solution used in Example 1 and collected on the screen in the same manner as in Example 1 except that the spinning nozzle shown in FIG. 6 was used, and the dimensions and spinning conditions of the spinning nozzle were as follows. Determined together.

[Dimensions of Used Spinning Nozzles]

(1) Inner diameter d of the nozzle 3: 0.3mm

(2) Length (s) of the protrusion of the nozzle 3: 5.0mm

(3) Pitch (p) of nozzle 3: 2.0mm

(4) Number of spinning liquid supply nozzles: 270

(5) Slit gap of air nozzle 6 (c): 3.7mm

(6) Length of rectangular to prism type slit in short axis direction (t): 20.0mm

(7) Length of rectangular to prism type slit in transverse direction (ℓ): 570mm

[Radiation condition]

(1) Amount of solution per single nozzle (3): 5ml / h

(2) Speed of air in the slit of the air nozzle (6): 54m / s

(Pressure: 2kg / cm ² , temperature: 18 ° C, relative humidity: 40%)

The collected fibers were calcined at 1260 ° C. for 1 hour to obtain alumina fibers having the following physical properties.

Diameter of the fiber: 6.6μm

Content of shot: 1 wt%

Bulk Tensile Strength: 1.8kg / cm ²

As a result, since the spinning nozzle of the present invention has the above-described specific structure, it is possible to produce an excellent fiber having no mutual adhesion between the fibers, uniform quality, low content, and high bulk tensile strength. In addition, according to the spinning nozzle of the present invention, it is possible to considerably reduce energy costs (amount of air used) and to produce fibers having good quality. Thus, the industrial value of the present invention is surprising.

Claims (6)

In a spinning nozzle for dry spinning a spinning solution containing a metal compound and an organic polymer compound by a blowing method, the spinning nozzles are vertically arranged cover plates each having a blade edge, a rectangle formed between these two cover plates. A prismatic slit, and a plurality of spinneret feed nozzles, wherein the feed nozzles each consist of linear conduits, positioned within the slit such that the nozzles extend parallel to the opposing surface of the slit and protrude from the space of the slit. Spinning nozzle, characterized in that. 2. The path of claim 1 wherein the gas chamber is formed in each of the two cover plates arranged vertically and a path is formed in each of the cover plates such that the path is perpendicular to the slit while extending from the gas chamber to the rectangular-prismatic slit. Symmetrical spinning nozzle. 3. The spinning nozzle of claim 2, wherein the path comprises a horizontal space and a vertical space, wherein the cross-sectional area of the horizontal space is smaller than that of the vertical space. 4. The spinneret according to claim 3, wherein the cross-sectional area of the path of the inclined space is gradually reduced in the gas flow direction while the path further includes the inclined space. The spinneret supply nozzles each consist of linear conduits, with two cover plates with blade edges arranged vertically so that these nozzles extend parallel to the opposing surfaces of the rectangular-prism slit and protrude from the space of the slit. Contain a metal compound and an organic polymer compound through the spinning liquid supply nozzle while blowing air through the rectangular-prism slit using a spinning nozzle comprising a plurality of such supply nozzles positioned in the slit formed by the Method of producing a fiber precursor of a metal compound comprising the step of extruding the spinning solution. A method of producing a fiber of a metal compound, comprising calcining the fiber precursor claimed in claim 5 at a temperature of 700 to 1400 ° C.