JPS5976923A - Manufacture of carbon fiber - Google Patents

Abstract

PURPOSE:To obtain continuous carbon fiber by the melt-spinning of a pitch-based raw material, by attaching a liquid to the spun fibers under specific condition, collecting the fibers, making the fibers infusible, and thermally carbonizing in an inert gas atmosphere. CONSTITUTION:Fibers obtained by the melt-spinning of a pitch-based raw material, preferably made of coal or petroleum pitch, are passed through two or more rollers made of e.g. metal and one or more destaticizers of preferably corona-discharge type, and taken up with an air sucker. The fibers are imparted with a liquid such as water, urea etc. in the air sucker or immediately after the sucker, and collected. The collected fibers are made infusible by oxidizing with air, and thermally carbonized in an inert gas atmosphere to obtain the objective continuous carbon fibers. The liquid is preferably the one inert to the fiber and capable of giving collectability and antistaticity to the pitch-based fibers.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing long carbon fibers using pitch-based raw materials.

Conventionally, pitches have been consumed in large quantities as starting materials for coke and carbon materials, and it has been devised to use all of these raw materials to produce locust fibers, which are now industrially produced in large quantities. Carbon fiber can be roughly divided into two methods: one is made from acrylonitrile-based synthetic fibers, and the other is made from melt-spinning pitch-based raw materials.The former involves wet-spinning long fibers of kMP+ fibers to produce the desired product. The process involves continuous processing of rainbow-dressed fibers, and the standard shape of the product is that of long fibers. 1Ur5'rAPI chopped fiber (short fiber) for face or pinch type carbon, or it is processed into 2T-fiber products such as twisted yarn, felt, cloth, paper, etc. as raw materials, mq 11:
As a product that is aligned in the length direction, the shape is at best that of a sliver. This means that when collecting yarn for carbon fiber by melt-spinning pitch system, the melting viscosity di of kj P+ depends on 1 degree? Due to the extremely steep slope of t°C, the safe operating temperature range without yarn breakage in the spinning VC is increasingly narrow, resulting in slight irregularities in temperature control or, in some cases, defects in the spinning work area. ``There is a risk of thread breakage due to drag-related fluctuation factors, for example, factors such as the flow of minute air currents.
Endless long fibers like synthetic fibers produced by four-way melt spinning of nylon and polyester * n
＜It is a prefecture that has difficulty in collecting income. Furthermore, since the spun carbon stitches 1a + u ht are also fragile,
In the usual melt spinning method, yarn j7j is generated frequently, and long fibers υ and pitch fibers cannot be found. ,#
It is no exaggeration to say that he is completely incapable of handling fibers that are conventionally used, such as rewinding, as is the case with general synthetic fibers. Therefore, even though it is desired to produce carbon fibers in the form of long fibers, the actual situation is that the shape of short fibers has to be avoided. One of the most common manufacturing methods currently in use is pitch dyeing, which is discharged from a molten table spinning nozzle. Once it is made into a fiber and wound onto a rotating bobbin, a
As mentioned in f1, since the yarn itself is fragile, it can be wound open, so it is possible to wind it very thinly and replace the bobbin as appropriate.
The obtained thinly wound raw yarn is cut into 9 pieces, for example, into two parts to form a sliver, or alternatively, the melt is shaken off by centrifugal force from a nozzle in a secondary centrifugal spinner and collected in a basket, and then usually After applying the so-called heat oxidation infusibility treatment that is carried out in the manufacturing process of pitch-based carbon fibers, the entire carbonization treatment is performed in an inert gas atmosphere, and the product is produced by cutting to the desired fiber length. The only difference, if any, is that the chopping step to form this final product is performed before or after infusibility.

Pitch-based carbon fibers can be roughly divided into low-strength, low-elasticity, so-called low-grade, and high-strength, elasticity...eblades.
It is made by a method of liquid crystal spinning of in-metho-phase or brimethophane. If you can obtain the highest quality in either type or filament state, you can expand the usage.
There is a huge contribution to the elimination of waste by increasing product yield in the manufacturing process. M is a low-grade large potential Wd essential? For example, in the use of asbestos substitutes for asbestos materials, brake materials, insulation materials, cement building materials, etc., and axle structural materials mainly for automobiles, for example, glass fiber is a typical example. If roving, which is a product mark, can be created, the manufacturing process will be more rational than VC, and a wide range of processing techniques using pitch-based carbon fibers will become available.

Those who want to obtain long-fiber carbon fiber from pitch-based raw material have failed as a result of 4νr research (jlr: completed).

An object of the present invention is to provide pitch yarn carbon fibers in the form of long fibers. Another object of the present invention is to provide a method for manufacturing such fibers industrially and easily.

In the method of the present invention, the pitch base material 1'lk is melt-spun by at least two rotors and at least one static eliminator 111fI: air 'L''j'-1, which is taken up through the car. , Immediately after passing through the eggy sucker or the d-tech τ-sucker, a liquid is applied to collect and collect the yarn, which is oxidized in the air to make it thermally infusible, and then heated and carbonized in an inert gas atmosphere. shall be.

Pitch base launch applied to this launch 1 1. In this case, tar 1 is obtained by dry distillation of organic substances such as coal, and not only the black carbonaceous solid residue obtained during distillation, but also the carbonaceous solid residue obtained during distillation, as well as the carbonaceous solid residue that is removed as a solvent during the coal liquefaction process called SRC or the tar extraction process. Solid content and stone AI] Heat-treated products of asphalts can be mentioned. Pitches prepared by thermally decomposing polymers such as polyvinyl chloride and low-molecular weight organic compounds such as tetrabenzo7-enazine, as well as any of these bicarbonates, can be heat-treated in an inert atmosphere to produce optically anisotropic FM mesofaces. , those formed with pre-mesofaces are also included.

In @melt spinning of pitch-based raw materials, the lamp-spun raw yarn is fragile, so it is impossible to collect it thickly onto a bobbin like the usual melt-spinning synthetic fibers. An air sucker is used to collect the fibers, and the fibers are passed through the air sucker through at least two rollers and at least one static eliminator with the help of air flow, and stored in a 71 ipper gun without damaging the fibers. The rollers used here are Kagami IIIJ and Higemata Vi satin finish metal 1J.
Typical rollers are +- and +-quality, with rubberized surfaces,
Even those covered with resin can be used. It is preferable that one roller t is placed 10 degrees below the vertical line than the normal spinning wheel, and the roller 111 is positioned as appropriate depending on the working situation. One of the other rollers is used for pulling the fiber into the fiber can.The fiber dancer is usually made of a perforated cylinder and is mounted on a disc that rotates concentrically on the floor. place

The pitch-based raw material is hydrophobic due to its ellipsoidal components, and the raw yarn produced by melting it and discharging it does not exhibit water absorption. Therefore, after leaving the spinning nozzle, during the process of passing through at least two low twos and an air sucker, a considerable amount of static electricity is generated between the R fibers and the R fibers due to contact between the #i fibers and between the fibers and other materials. As long as the work is electrically charged and the work is continued as it is, the fibers will not wind up in a low state. In recent years, the collection has been done without rice, and each single fiber has become A-matched, making it completely impossible to transfer it to the next process with the thread shape ratio.

In order to eliminate static electricity and focus the filaments, an oiling method such as that used for ordinary synthetic fibers, such as UL, in which all running fibers are brought into contact with a rotating roller with an oil film attached to the surface.
In this case, this method will not be adopted at the end of the month because the spun yarn is fragile. Due to the resistance that the spun yarn receives when passing through stratified layers made of various oils, the yarn is mostly spun/slipped.
The Vc stress is transmitted and most of the 74 strands are cut at 7 points.

In the misfire 91 method, the long fibrous yarn is stored in the 7-eye percence through an air sucker, and immediately before it is stored, it is applied with VCC liquid and used. In the process of entering the fibers, the friction between the fibers as they move, the focusing kite used if necessary, and the static electricity generated when they come into contact with at least two [l-2-] accumulates on the fibers, and as a result, the thread The disorder of the rows, the entanglement with the low sea, and the phenomenon caused by fz b bf go occur. In order to do this, at least one static eliminator 6 for the yarn 2 knee "C-→Notsker to 4 people" is reinstalled to actively eliminate the static electricity accumulated in the yarn. Eliminate the causes of these troubles and eliminate them. Static eliminator used in the present invention Wb If
: This is a V-electric charge (using hL's corona discharge type static eliminator, which is installed towards the running pitch-based fiber system), and depending on the electrostatic #A generation group of lJ & miscellaneous, it is The +i voltage current capacity of the eliminator, the shape, number, installation position, etc. of the static eliminator may be easily selected keeping in mind the traveling type, and there is no limit to this.

Normally, the static eliminator is preferably installed immediately after the pitch yarn fibers pass through the convergence guide and immediately after each row passes.

In this way, the pitch-based fibers are made into an air sucker and stored in a fiber can by spraying with a VC spray nozzle, or by injecting a liquid from the vicinity of the yarn suction hole or air introduction hole of the pitch-based fiber. Apply liquid to the yarn surface.

It is best to apply the liquid by spraying it onto the surface of the pitch-based fiber yarns immediately after passing through the air sucker.

Pitch-based fibers whose surfaces are dripped with liquid do not completely absorb the liquid, but instead a large number of filaments adhere to each other and converge. The fibers are then stored in a rotating fiber can as long filament yarns that remain bundled.

As mentioned above, the purpose of the liquid used here is to wet the surface of the hydrophobic pitch-based fibers and to coat multiple pieces of fikumen l-1.
The role of the liquid is not simply to make a single fiber bundle. That is, when producing the final target carbon fiber from pitch fibers, as described later, the fibers are first oxidized to make them heat infusible, and then heated to a predetermined temperature in an inert atmosphere to produce the target N& However, in carrying out this process, the nine-pitch fibers are melt-spun and shaken directly onto a movable metal or ceramic conveyor, or they are once stored in a predetermined amount using a seven-eye percence system. After that, in order to fit the shape of the final product, the pitch fibers, which are made up of a single fiber bundle, are taken out again from the multiple 7-way fibers, and then the fibers are doubled and then oxidized. Take. No matter which process is taken, the state in which the product is fermented in the hedron immediately after spinning is accompanied by the quality of the liquid-containing dispersion due to drying over time, so as the content decreases, the cohesiveness decreases, and in extreme cases During movement on the conveyor or in the process of taking out the fiber bundle from the 7-way chain, fraying occurs between single yarns, which may lead to single yarn breakage.

If static electricity is generated due to friction between the fibers or the contact friction between the fibers and a device such as a roller during the movement of the fiber bundle across the length, the bundled fibers will collapse again and the single fibers will be cut. Not only will this cause the problem, but it will also become impossible to create the desired long-fiber carbon fiber. As described above, the face piece intended for the binding material used in the present invention does not merely seek the effect of imparting bundle properties immediately after spinning, but also allows the pitch-based fibers to be left for an unspecified period of time after spinning. Immediately after, it is necessary to exert a similar focusing effect, and also to have a training effect to suppress the generation of static electricity when the fiber bundle is connected.

110, while unexploded 4 K 2 Pitch raw materials used: As defined above, 1111 are coal-based, petroleum-based, heat-treated products thereof, organic polymers, and pyrolyzed products of emulsifying compounds. Naturally, liquids containing active substances that act on these substances and physically or chemically alter them cannot be used. The effect mentioned here is that in the process of touching the joints of the pitch fiber surface at room temperature immediately after spinning, the pitch fiber itself causes swelling and sticking, and also causes a phenomenon 1 such as partially dissolving at the ends of the pitch fiber. Needless to say, pitch-based materials can be used under the conditions of an atmosphere of around 600°C in the air during infusibility treatment, which is a process after spinning, and a maximum temperature of 800 to 2000°C in an inert gas atmosphere during carbonization treatment. Substances that have the effect of causing fibers to stick together or partially dissolve must be avoided.

The liquid applied to the pitch-based fibers in the misfire 1 is basically (1) inert to the pitch-based fibers, and (
2) Z) It imparts convergence and antistatic properties to the fibers, and (B) It does not remain as ash after carbonization. As such a liquid, an aqueous solution of an inorganic or organic compound is suitable. These compounds are (1) water-soluble and remain soluble at room temperature, (2) hygroscopic in room air,
It is preferable that it has a deliquescent to deliquescent property and that it evaporates and decomposes and disappears at temperatures around F4 in air (9 degrees Celsius).In addition, during the infusibility treatment process of pitch-based fibers, it is preferable that the particles adhere to the fiber surface. It would be even more desirable if the presence of solutes could also contribute to promoting pitch oxidation.

Organic compounds that meet these conditions include ethylene carbonate, ammonium carbamate, ammonium citrate, citric acid, ammonium oxalate, ammonium formate, ammonium acetate, ammonium succinate, isocyanic acid)' Inorganic compounds include ammonium carbonate, ammonium hydrogen carbonate, ammonium nitrate, ammonium thiocyanate, ammonium cyanide, and ammonium hydroxide.

Conditions for these compounds d above (1) to (5)? Among them, for example, ammonium nitrate is decomposed into a gaseous body at 210°C, and in the decomposition process there is a catalytic effect that promotes air oxidation of pitch. It is suitable because it has.

In any case, these compounds can be used alone, and iJ2 can be used in combination of two or more, but it all depends on the conditions of use in water tts r&. Solution concentration t/'i2.01 in that case
A range of % below JL is preferred, and a range of KO, 05 to 10% is preferred.

In the method of the present invention, as described above, the liquid present in the pitch yarn fibers is preferably an aqueous inorganic or organic compound. For example, can you seal the container and let the water evaporate? Water alone may be used when suppressing or when it can be sent to the next process immediately after collection. Depending on the spray method, pitch + lll1. For attaching the focusing liquid to the fiber surface, use 0.2 to 4 to pitch acid #11.
% by weight is preferred, particularly preferably 0.5 to 2% by weight. The core control of the focusing liquid adhesion sheet is determined by adjusting the amount of the spray and the distance of the spray zone to be sprayed onto the traveling pitch-based fibers.

(VcIP, an example of yarn spinning and take-up, will be explained with reference to all the drawings, but it will not occur) This is not intended to be limiting in any way.

That is, in Fig. 1, the female 1 is a spinning nozzle housed in the spinning device, and the raw material pitch is heated and melted and discharged into the air from this nozzle at a spinning speed of 100 to +500 m.
/- to spin. 2-piece focusing guide, Roha take-up roller, 4#'i final take-up roller, 5-piece air sucker,
Reference numeral 6 designates an e-electrostatic eliminator, 7 a liquid jet M/zole, 8 a cylindrical fiber can, 9 a housed long fiber pitch fiber, and 10 a rotating disk.

Squeeze the pitch fibers discharged from the nozzle as necessary.
5.4. The fibers are taken up by a rotating roller and suctioned with an air force of 5, applied to the fiber surface 11 by using all the spray nozzles 7, and stored in a fiber container 8.

In this case, the fiber cans 8 are installed on the rotating inner plate 1o so that their centers are aligned with each other, and the nozzle of the air sucker 5 is located at one end of the center of the Wtli rotating disk 1o and one end of the 7-eye perguns 8. The nozzle may be installed at a height of 1 m on a vertical line, or the nozzle may be placed at a position between the center of the rotating disk 10 and one end of the fiber can 8 when the nozzle is moved in a spatial position other than above the fiber can 8. Set it to . Further, if necessary, the air sucker nozzle 51j may be provided with rotation interlocking 4 horizontally or cylindrically.

In this case, the suction hole diameter, length, etc. are selected as appropriate depending on the total number of A'-Zucker 5# threads used and the spinning speed.
History Vc also includes compressed air pressure, air volume, etc. for air soccer.
Choose as you like. It should be noted that the static electricity iL6 charged by the friction of the running yarn during this period of VCss is actively removed by a removal device.

For example, when applying a girdle to the fiber surface before a take-up roller, as in the case of spinning synthetic fibers, the cohesive force of the liquid acts on the brittle fibers of the pitch-based fibers involved in Kinoe Ida1. The yarn wraps around the roller and smoothly reaches A-Sotsuka-54 Beniyama 7 and 8. At the same time, drop the liquid at the point where the fiber yarn is suctioned with at least -5 force, or
Blow into Air Datsuka-5! Either by conveying it to the secondary air and sending it into the nozzle in the form of a liquid, or by injecting the liquid into the nozzle structure immediately after the inlet of the compressed air.
Otherwise, the yarn will be completely absorbed by the air sucker 5, and the long fiber hitch yarn fiber 9 thus stored in the fiber can 8 will not be separated into a single yarn at all, and will be completely formed into a single yarn. It is a remarkable phenomenon that the fibers are held in a loosely stacked state in a spiral shape, and the fibers can be collected without being exposed to 4T4 scratches.

The method of spinning an extremely brittle, hydrophobic material using fully bundled long fibers has not been known in the past, and the method of the present invention is the first time that it has been successfully applied. Surprisingly, the fragility of each wheel yarn has not been improved in any way, but it has been found that the fragility of each thread has not been improved in any way, but it is It has become clear that it can be handled in the same way as ordinary fibers.

That is, if necessary, it is possible to hold the pitch fibers 9 in the fiber can 8, and also to combine them with the other B1, and also to make one skein by passing them through the spinning wheel of the rotating part. It can also be rolled up.

The pure fibrous pitch fibers once stored in the fiber cage as described above are then subjected to oxidation treatment to change them into a heat-infusible state. There are two types of oxidation treatment: a dry type that mainly uses air, and a wet type that is performed in an oxidized face. Of these, heating and oxidation is the most popular method. Long M when you do it again! ．． Regarding the retention form of fibrous pitch-based fibers, it is basically a good idea to expand the fiber surface area as much as possible and bring it into contact with the agility.
A practical method for this is to loosely transfer the pitch-based fibers onto a metal mesh or perforated plate.
Another method is to proceed with oxidation from the surface of the fibers without moving the fibers in a heated atmosphere where air is present. Or 7
The eye pack itself consists of a wire mesh or a four-hole perforated tube, and the yarn in a predetermined area is stored in it, and the yarn at the end is threaded to form an independent loft. Or cut; connect it with a separate ken without vf, also known as ken, and seven ma\-
One way is to promote sanity oxidation. In any case, during oxidation, the gradient of 8Ml + 6JA in air is 0.6 to 10.
In the case of a hit consisting of ゛C/trend and optically isotropic m 3tt, the temperature is 20 to 150L lower than the softening temperature of the raw material pitch.
In the case of a pitch having an optically isotropic structure, the pitch is brought to a temperature below its softening point and maintained within its maximum temperature range for 5 minutes to 15 hours.

Even if the air in this same volume of air is still, the man can actively stir it or ventilate it.

It is also possible to actively introduce ozone into an oxidizing atmosphere.
It's J.

After the infusibility treatment, the long filament fibers are introduced into a heating area under an inert gas atmosphere and heated and carbonized to form shell fibers. The temperature gradient #'11 to 20' C7 allows movement of the temperature either under tension or under tension, and increases the temperature in the heating region.
The carbonization process is completed in 60 minutes at a maximum temperature of 800 to 2,000 C1 and a holding time of 60 minutes. Place 1! l! The latter fiber is carbon fiber with sufficient tensile strength, and it can be rolled up into a roving bag, for example, according to normal fiber handling methods! ] 1 is 0J ability.

In case of dud 11, the spun yarn is made fragile and has no wicking or water absorbing properties, and is introduced into an air sucker via a take-up roller. By carbonizing the long strands of carbon fiber that could not be obtained from conventional pitch yarn raw materials, the carbon The fields of application of m-fibers are wide-ranging.

A detailed description will be given below with reference to examples, but the failure is not limited to this.

Example 1 Coal cool pitch with an average molecular weight ht b o o and a softening point of 220°C is filled in a Bessel type Merck-type vessel, and heated from the upper part filled with nitrogen gas to form an inner M 26 (+'C, m rNQ Lπ Coal Cool Pitch was quantitatively fed by a gear pump and discharged out of the system from a spinning nozzle with a hole diameter of 0.5 fl and a number of holes of 56. In this case, a focusing guide is installed directly below the nozzle, and a corona discharge is applied between it and the @10 roller, as well as between the 9R1 roller and the 20th roller. A Static Eliminator 411!+ (Erimino Scutt, manufactured by Shishido Shokai) was installed to remove the static electricity charged on the long pitch yarn fibers, and then the air sucker was used to suck it in. A 2% lL mouse urea aqueous solution was poured under the nozzle surface of a pneumatic rotary type with a diameter of 8 pipes and a length of 150 m, and the fiber was gripped with a 15 wt% adhesion length per fiber weight on the curved surface of the fibers. I laid it down and stored it in a fiber can with a sakimaki fall.

The air lacquer nozzle was positioned on a vertical line between the center and the periphery of the fine can, which rotated concentrically at a speed of 7 i'/s rpm.

Spinning (spinning Ht time) Collect large pitch fibers in multiple 7-eye percense at intervals of 10 minutes, 1/&I, and after the end, take out a large bundle of yarns from 5 dances and combine them into 1 thread. After threading, the end threads are arranged in a meandering pattern on a stainless steel metal plate and passed through a heating furnace maintained at a maximum temperature of 500°C. /#lI+
, 500°C was maintained for 20 minutes. The yarn taken from the heating furnace remained unmelted even when exposed to flame. The infusible yarn was placed on a stainless steel wire mesh in a non-tensioned state and agitated in an electrically flowing nitrogen gas '5I at a center temperature of 1000°C. In the case of Jin, the temperature gradient is 5'C/Il'l! , highest IWK + 00
T) The long fibrous yarn was carbonized under conditions such that the C retention time was 10 minutes.Fur Cool Pitch was then used as a raw material and long 1 generation carbon fiber was collected. This fiber material has a fiber diameter of 16I and a tensile strength of 80L.
/a4, tensile modulus of elasticity 2900q/-tea-11hi.

As a comparative experiment, tj
When the fibers were spun under the same conditions, the fibers spouted from the egg twister were stirred up, and the single yarn phase change occurred. Even if it were to be soaked, it would remain in the form of a lump, and the long fiber-like filamentous part could not be collected at all. Ta,.

Examples: Solvent refined charcoal with an average molecular weight of 800 and a softening point of 245"C.
Abbreviation 5RC)' was filled into the same spinning device ft as in Example 1, and 4! t $, heated the inner temperature of the sealed top to 270 'C to melt it, u, discharged from a nozzle with 11111 holes of 15 m diameter, Table 1111 2 rollers rotating at a speed of 500 MI / M all but During the running of the fibers, two static electricity eliminators were installed in the same direction as in Example 1.
2 +&. Place the air sucker nozzle at a distance of 20 cm from the fiber can overhead side.

Rotate the nozzle direction from 1-j around the can.

It was installed at an angle of 176fζ of the can radius. A ringing device was placed directly below the air sucker nozzle, and a 0.5 weight percent aqueous solution of anthene nitrate was sprayed around the pitch fibers discharged from the air sucker nozzle. In this case, the injection amount was adjusted so that the adhesion on the focusing surface was 0.6%.

Thus, fiber surface with focusing liquid? 100 by moistening
The filament was made into a single bundled thread and housed in a spiral shape in a 71 Iverkens. A total of 10 bundled yarns of one tree were collected from 10 fiber cans, and they were combined into one long fiber-like yarn. Under the same conditions as in Example 1, first, they were heated in a mobile air conditioner. It can be heated to a maximum temperature of 270℃ in nine places, making it heat infusible without sticking to each fiber direction, and furthermore, the maximum hot water temperature is 1100℃.
℃ ramp rate 7℃/can, + l OrjiC
After being held for 15 minutes and carbonized, the fiber diameter was 14 μ, the tensile strength was 90 kQ/, 4, the tensile elastic band 521] mouth Af/-
& fibers were obtained in the long fibrous filaments. The resulting fiber can be rolled into a roping shape and touched.

In this case, without installing a discharge-type static electricity remover, only the above-mentioned focusing liquid was applied under the Wacker nozzle 1u.
When we adopted this method, 41 pieces of bi-nochi was discharged from the vJ thread nozzle! Fi static electricity was generated, and the thread ran.
The L yarn spreads to 4U, wraps around the surface of the 10th layer, and it becomes difficult to move the fibers up to the 161K position, making it impossible to collect pitch-based fibers as long fibrous yarns. Ill never come.

Example carbon content 90.2%, quinolinium solubles 1j%
of Glossia asphalt was packed into a 4-tube container, stirred thoroughly under a nitrogen gas flow, and then thermally decomposed for 6 hours while keeping the internal temperature at 420'C. The polycondensation was carried out at λ11, the softening point was 280°C, and the quinoline solubility was 411<if A mesoface pitch with an optically anisotropic structure of % was obtained.

This pitch is melted by keeping it at an internal temperature of 70°C.1. Hole diameter 01
Nozzle surface temperature 5 from 1 hole &2'io spinning nozzles
Maintain the temperature at 511 degrees Celsius and discharge it, use a focusing kite, and a static eliminator to remove the surface at 1 trillion degrees 600 m/x? +I+
The sample was brought into contact with a rotating roller sheath, and was then sucked into an air sucker nozzle via a static electricity remover and a take-up roller with the same surface speed. External force - Nozzle position I
M was the same as in Example 1.

As the focusing liquid, an aqueous mixed solution of 0.5% by weight of ammonium acetate and 4% by weight of ammonium hydroxide was used.

This water #'F liquid is pressurized at the bottom of the air inlet hole of the air sucker and applied to the surface of the pitch W & fibers sucked into the nozzle hole so that it adheres in the form of a mist to the surface of the fibers. 96, 41-1, and two bundled yarns were collected in a spiral shape inside the fiber kunsu.

The obtained fibers are 60% qa, and are left in a room at 25°C for one week before being combined. To do this, one piece of bundled yarn is taken out from four cans, and the yarn is wound onto a wire mesh via a guide. ·deer,
When t' was carried out, the convergence system of each tree was a single yarn Vj due to static electricity generation V5: a state of convergence during spinning without any curling phenomenon1
．．・The total number of filaments is 1000 in the shape of i2. This resulted in the creation of $, which can be stored and handled as a long fibrous yarn.

This thread was passed through a heating furnace held at a maximum temperature of 240"C for 1 hour in the presence of air.
・Destroy it and make it heat infusible, +80 to the thread of -f: to the history
Transfer the mixture to 11°C under a nitrogen stream atmosphere.
For the first time, the fiber-like carbon fiber had physical properties of 1'' diameter of 10 μ, tensile strength of 195 mm Q/a4', and tensile modulus of 18.00 tl Kq/-.

In addition, in accordance with this application example, we installed a discharge type static electricity remover.1
Also, in the egg sucker nozzle, the focusing shield 1ζ1
Give? When the yarn was spun without fj, first of all, the pitch yarn #R fiber was wrapped around the 10th sea. It was not possible to collect it as a pure fibrous thread.

4, Figure i1o ] 17. ＋ Fit i explanation" Figure 1 Nihon #Collection; Kun is an example of a dud implementation hoe? FIG. 1 is a diagram illustrating the spinning method shown in FIG.

Claims (1)

[Claims] (1) Is it suitable for melt-spinning Hitachi base material PI', at least two rollers and at least one static eliminator? The entire eggyp car is picked up through the air sucker, or immediately after passing through the air sucker (the threads are bundled and collected by air oxidation to make them infusible, and then inert. A method for producing long* fibrous pitch-based carbon fibers, which is characterized by carbonizing the fibers by heating in a gas atmosphere. (2) The method according to claim 1, wherein the pitch-based raw material is a coal-based or stone-based material. Method. (5) The method according to Claim 1, wherein the static eliminator is a corona discharge type. (4) The method according to Claim 1, Jr. 4, wherein the liquid is inert to pitch-based fibers. ( 5) The method according to claim 1, in which a liquid imparts focusing properties and conductive properties to pitch-based m-fibers. (6) The method according to claim 1, in which the liquid is aqueous. (71 Feature fI applied by full liquid spraying - method according to claim 1. (8) IF#IP in which thermal infusibility is carried out at a heating rate of 0.5 to IO"C/III/l The method described in claim 1. (9) The method described in claim 1, wherein carbonization is performed by heating at a temperature of 800 to 2000°C.