JPS62123007A - Production of raw material for composite molded article of carbon type - Google Patents

Abstract

PURPOSE:To obtain a raw material for producing composite molded article of carbon type having characteristics such as high strength, high-speed carbonization properties, dimensional stability, low electrical resistance, etc., by susending a specific material in a tar fraction containing a mesophase pitch precursor and heat-treating the suspension under an inert gas circulation or under reduced pressure. CONSTITUTION:A metarial selected from graphite carbon, carbonaceous carbon, inorganic compound and metal (compound) is suspended in a tar fraction containing mesophase pitch precursor. Then, the suspension is heat-treated by introduction of an inert gas or by suction under reduced pressure at 350-520 deg.C. A light traction contained in the tar fraction is distilled away to give a raw material for composite molded article of carbon type wherein a mesophase-containing pitch having 2-90wt% quinoline soluble content is formed on the surface of the material. This method has merits wherein a high-strength molded article is obtained even if a ratio of the mesophase-containing pitch to the material is low and properties of the molded article can be widely changed by selecting the ratio and molding condition.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention provides a mesophase containing pitch using one or more materials selected from graphitic carbon, carbonaceous carbon, inorganic compounds, metals, and metal compounds. This relates to a raw material for a carbon-based composite molded body coated with.

[Prior art]

In general, when producing carbon materials such as graphite electrodes, aggregates such as coke that do not have caking properties by themselves and cannot be pressed into compacts are used for 100 t parts of aggregate. A widely used method is to add pitch of 30 to 40 weights as a binder, and to perform the steps of kneading, molding, and firing. However, in this case, a slow heating rate of approximately 1°C/hr is required in the temperature range of 300 to 600°C where the binder pitch melts and carbonizes, and the pitch carbonization yield is as low as 50 to 60%. There are problems such as the formation of a large amount of pores and the need for re-impregnation with binder pitch and secondary firing in order to impart density.

In order to solve these problems, various improvement methods have been proposed; for example, in Japanese Patent Application Laid-Open No. 52-24211,
An improved technique for mixing aggregate and binder pitch is described.

The publication describes that carbonaceous or graphite powder is mixed with pitches, this mixture is heated at 350 to 450°C, and the mesophase produced from the pitches is added to 1 part by weight of carbonaceous or graphite powder. Carbonaceous molding can be achieved by separating the carbonaceous or graphite powder and Men7Aze from the pitch, pressing it as it is, and firing it. In the method for producing pitches, or when heat-treating the pitches, the carbonaceous or graphite obtained after heat-treating so that almost the entire surface of the pitches transitions to mesophase is crushed, and the men7Aze is processed as is. A method for manufacturing a carbon molded body made of carbon or graphite to which mesophase is attached is disclosed, which comprises pressing and firing.

The method has the following characteristics: (2) Since the mesophase adheres around the additive, there is no need for a crosstalk step.

(11) Since Men7Aze has a high carbonization yield and does not pass through a softened and molten state during carbonization, a temperature increase rate of 100° C./hr or more can be achieved.

(iii) Since the mesophase generated in the pitch penetrates into small gaps in the carbonaceous material and graphite material, the porosity of the carbonaceous material and graphite material itself does not affect the carbonized molded product.

etc. are listed.

In addition, in Japanese Patent Publication No. 58-39770, carbonaceous aggregate,
From the nurary consisting of bituminous material and liquid medium, all or part of the liquid medium soluble matter is separated to separate the solid matter,
This solid material must be heat-treated after being pressure-molded! A method for manufacturing a carbonaceous molded body characterized by i- is disclosed. The aggregates used are various types of coke, natural graphite, artificial graphite, and cargomp2. It is preferable that the powder be made of carbon fiber or the like, and contain at least half of the powder that passes through a 200 micron sieve. The bituminous materials used as binders include coal tar, coal tar pitch, petroleum hit, asphalt, and mixtures thereof.In the present invention, these bituminous materials are converted into so-called r-resin (quinoline resin) by physical and chemical methods. soluble,
It is characterized by using a product from which all or a portion of the benzene soluble content has been removed.

Conventionally, it was difficult to spread the binder pitch sufficiently over the surface of the carbonaceous fine powder, so even if fine powder was blended to obtain a dense and strong product, it was not possible to obtain a homogeneous molded product. By using this method, it becomes easier to uniformly disperse the effective viscous components in the bituminous material in all the fine powder. Car yj? hmm! When using ultrafine powder such as rack, the conventional method Whereas a separate step was required to spread the adhesive component over the plastic surface, the method of the present invention has advantages such as simultaneous immersion. Also, conventional 3
The process that used to take ~6 months can be shortened to 7 to 10 days using this method, which also allows direct graphitization, and the harmful dust and mist generated in conventional processes such as kneading, cooling, and secondary crushing can be eliminated by this method. It has also been shown that it has the advantage of being able to maintain a good working environment because it can be dissolved and removed in an organic medium.

In addition, the present inventors have noted in Japanese Patent Application Laid-Open No. 52-24211 that some graphite materials can be formed into compacts by pressurization. A volume resistivity of 5mr1y1 characterized in that the powder obtained by mixing the powder with a pitch powder containing Mbuez in the same amount as the powder is pressure-molded to obtain a green body, and the green body is further fired at 700°C or higher in an inert atmosphere. Hereinafter, we have proposed a method for producing a molded body having a bending strength of 200 ψ or more, a volume change before and after firing of 3% or less, and a weight change of 3 cm or less (Japanese Patent Application No. 199737/1983). The graphite molded body obtained by this method has been shown to be suitable for use as a cell member for a phosphoric acid type fuel tH1 tank, for example.

[Problem that the invention seeks to solve]

In the method described in JP-A-52-24211, a large amount of mesophase vinyl is used in an amount of 0.3 parts to 1 part of carbonaceous or graphite to obtain a molded body.

However, the mechanical strength of the obtained molded product is not necessarily high. This is due to the fact that the viscosity is not sufficiently high because the produced men7Azubi and chi are essentially quinoline dissolved components, and that the viscosity is not high enough, and the carbonaceous material is mixed with comparatively high viscosity pitch and carbonaceous or graphite. Alternatively, this may be due to the fact that the impregnation of pitch into graphite is not necessarily sufficient.

In addition, in the method that involves separating a large amount of pitch with an organic solvent such as quinoline after mesophase generation, it is necessary to wash the separated mesophase and coke with benzene and acetone and then dry them under reduced pressure. However, from a process perspective, it requires complicated processing steps related to the kneading step.

On the other hand, in the method described in Japanese Patent Publication No. 58-39770,
It is clear that new problems arise in the process, such as the need for organic solvents such as benzene and toluene, which are 20 to 50 times the amount of aggregate, and the need for a recovery process for r-reson. be. Further, the invention does not mention anything about coating mesophase pitch.

Furthermore, the method previously proposed by the present inventors in Japanese Patent Application No. 59-199737 had the problem that the process to obtain mesophase-containing pitch powder was long.

[Means for solving problems]

(Object of the invention) The present invention was made in view of the above situation, and
The purpose is to use one or more materials selected from graphitic carbon, carbonaceous carbon, inorganic compounds, metals, and metal compounds with high adhesiveness and in a wide range of quantity ratios to the mass of the material. It is an object of the present invention to provide a method for producing a raw material for a carbon-based composite molded body coated with mesophase-containing pitch that can be used. This raw material is suitable for producing a carbon-based composite molded article having characteristics such as high strength, rapid carbonization, dimensional stability, and low electrical resistance.

(Structure of the Invention) That is, the present invention provides: 1. A carbon-based material comprising one or more materials selected from graphitic carbon, carbonaceous carbon, inorganic compounds, metals, and gold ellipsoids and mesophase-containing pitch. In the method for producing a composite molded body, (1) one or more materials selected from graphitic carbon, carbonaceous carbon, inorganic compounds, metals, and metal compounds, total mesophase pitch of 6tt W, tar fraction containing metal; The process of suspending

(2) The turbid system is heated for 1 d, and the light fraction contained in the tar fraction is distilled off by blowing inert gas or vacuum suction to remove the men-7-pitch precursor. 350-52
A step of obtaining a carbonaceous precursor which is heat-treated at 0° C. to produce menphase-containing pitch containing 2 to 90% quinoline soluble content on the surface of the material.

A method for producing a raw material for a carbon-based composite molded body, characterized by using the following two steps.

(Detailed Description of the Invention) (1) Step of suspending the material in a tar fraction The material (hereinafter sometimes abbreviated as "filler") used in the present invention from which mesophase-containing pitch is to be precipitated will be described.

Examples of the graphitic carbon include scale-like natural graphite, earth-like natural graphite, artificial graphite, and graphite fiber. In particular, the method of the present invention is characterized by a graphite powder that can be formed into two molded bodies by pressure molding at room temperature (for example, Nippon Graphite Industries II (II) CPB and ASP-1000).
Product name) +LONZA KS-2,5 (Product name)
) can be mentioned. Examples of carbonaceous carbon include petroleum coke, coal coke, carbon black, carbon peas, and carbon fiber. Examples of various inorganic compounds include silica-alumina, r-alumina, α-alumina, silicon carbide, and silicon nitride. Examples of metals include iron, copper, zinc, pots,
2. Kel, cobalt, lead, aluminum, gold, silver, titanium, platinum, no! Examples include radium. Part or all of these metals may be present as metal oxides or metal compounds up to the stage of slurrying and the stage of inclusion in the formed form.

Moreover, as a metal compound, for example, Fe 20. ,Zn
O, CuO1Cu C12, Zn Cl 2.5nC1
4, AI CI , TiCl4, Cu(No3)2, and the like.

In carrying out the present invention, even if only one type of filler is used, two types of fillers may be used.
A mixed system of i or more can also be used. Specific examples of mixed systems of two or more types include graphite and carbon, carbon and inorganic compounds,
Examples include combinations of carbon and metal. Examples of combinations of fillers include carbon pre-plated with metals such as copper and nickel.

There is no need to limit the type of tar fraction that is the raw material for the mesophase-containing pitch used in the present invention; coal-based tar,
Any petroleum tar can be used. Any tar fraction that can provide a menphase-containing pitch containing 5 to 90% by weight of quinoline solubles under operable reaction conditions may be used, but the properties required for the final product may be used. Tar species may also be selected by For example, when contamination of heavy metals, sulfur, etc. into the final compact is to be avoided, ethylene heavy end tar obtained by naphtha decomposition is preferable to coal tar or petroleum heavy component tar.

In addition, if the material has a large oil absorption area and a slurry cannot be formed even if an attempt is made to use only the tar distillate containing the mensueze pitch precursor, an appropriate solvent, such as a tar distillate recovered in the heat treatment process, may be used. Light fractions, quinoline, etc. can also be added as appropriate.

Further, stirring of the filler to the tar fraction may vary depending on the type of the tar fraction and the filler, and is selected so that the amount of mesophase-containing pitch covering the filler falls within the range described later.

For turbidity, the usual method is used, but if the needle contains some moisture that may prevent the tar fraction from completely soaking the filler surface, dry and degas it in advance. It is preferable. Furthermore, if the difference in specific gravity between the tar fraction and the filler is large, it is desirable to avoid separation of both components.

(2) Production process of mesophase pitch on the material surface The mesophase-containing pitch that meets the requirements of the present invention is produced by heating a slurry consisting of tar fraction and filler at 350 to 520°C.
Preferably, it is produced by heat treatment in the reaction range of 380 to 500°C. At this time, the slurry is heated under a flow of an inert gas such as nitrogen gas, carbon dioxide gas, or argon, or
The temperature is raised to the reaction temperature under a reduced pressure of 00 mxHg, maintained for a predetermined time, and then cooled to obtain a composite in which the surface of the filler is coated with mesophase-containing pitch. The amount of pitcher containing Men7Aze in the composite is 3 to 3000 parts by weight per 100 parts by weight of filler. In addition, in order to keep the volume shrinkage small when the composite is carbonized after molding, 3 to 50 parts by weight, preferably 5 to 40 parts by weight, more preferably 10 parts by weight.
~30 parts by weight.

Quinoline soluble minute needle of mesophase containing pitch is 2 to 90
Weight%. In particular, in order to obtain a dense molded product at a low molding temperature, 5 to 90 weight'ff (%, preferably 20 to 7
It is 0% by weight. On the other hand, in order to reduce volumetric shrinkage during carbonization, a relatively small range of quinoline soluble content is selected. Furthermore, in order to obtain a dense molded product with low volumetric shrinkage, it is desirable to select a pitch that has a large quinoline soluble content and a large mesophase content.

In the method of the present invention, since the heat treatment is carried out under an inert gas flow or under reduced pressure, light fractions in the tar are distilled off regardless of the type of tar used, resulting in a mesopoeze precursor having a relatively uniform composition. The mesophase produced is relatively homogeneous, highly sticky, and has a high carbonization yield. However, in order to obtain a pitch having a large quinoline soluble content and a large mesophase content as described above, it is desirable to use the following method already disclosed by the present inventors. That is, as raw material tar, JP-A-58-154792, 58-
As disclosed in No. 154793, No. 60-179493 and JP-A-59-97183, No. 59-97184, those having aromatic hydrogen content within a specific range, or tar fractions are treated in the presence of pressurized hydrogen or It is desirable to use one that has been reformed in the coexistence of pressurized hydrogen and a catalyst.

Further, in the heat treatment, the method disclosed in JP-A-59-155493, in which a compound having hydrogen-donating ability is blown into the reaction system together with an inert gas is more effective.

If the quinoline soluble content is too small, the strength of the carbonized molded product cannot be obtained when molded at a low temperature of 400° C. or less, which is not preferable. On the other hand, if the quinoline soluble content is too large, gas generation during carbonization will become significant, resulting in the formation of bubbles and deformation during carbonization, which is not preferable.

Note that the heat treatment temperature of the mesophase pitch precursor was 350°C.
If the temperature is lower than .degree. C., it takes a long time to form a mesophase, which is unfavorable from the viewpoint of processing and controlling the amount of quinoline solubles. In addition, when the temperature is higher than 520°C, higher-order polymerization of the quinolinated component is promoted, and the quinolinated component with properties similar to coke exists, making it suitable for hot melt molding as the object of the present invention. This is not preferable since it becomes impossible to obtain the containing pitch.

The amount of quinoline soluble content can be measured using the JIS-K2425 centrifugation method, but in the case of a complex with a fine filler such as carbon black, carbon black does not settle even after centrifugation, so it is removed as the quinoline soluble content, which may cause errors. Therefore, the following method was used to completely capture the fine particles and measure the amount of quinoline soluble content.

Approximately 1 y of a composite of mesophase-containing pitch and carbon black (the abundance ratio of both is calculated from the weight balance before and after the heat treatment reaction) ground to about 100 mesh or less using a vibration mill was accurately weighed, and a 50 m1 Erlenmeyer 7 with a stopper was placed. Add 30 m/i of warm quinoline to it, stopper it, and bring it to 80°C.
The quinoline-soluble components were dissolved by applying ultrasonic vibration for 30 minutes. A glass with a permeation particle size of 2.7 μm that had been adjusted to a constant U in advance.
The lath fiber filter paper was attached to a Whatman 3-bead filter funnel, the whole funnel was kept warm at about 80°C, and the slurry in which quinoline had been dissolved was poured into it, and the quinoline soluble content was removed under reduced pressure with a water pump. IJ was separated. Next, all residue on the d+'J paper was washed 3 times with warm quinoline 3Qmi, washed twice with 30 vtl of acetone at room temperature, air-dried with a stream of air, and dried at 150°C in a vacuum dryer until the paper had a constant weight. It was dried and the residue was determined. The total amount of soluble quinoline (by weight) was calculated from the amount of mesophase-containing pitch contained in the composite IP.

The composite of filler and mesophase-containing pitch produced in this process is composed of filler and mesophase class 11 and 'i
]1 can be obtained in powder form.

Even if it is stuck, it can be crushed by a simple means such as a beer mill if necessary.

The composite obtained by the method of the present invention can be made into a carbon-based composite molded product by pressure molding and carbonization. The molding temperature is room temperature to 800°C, and the carbonization temperature is 700°C or higher, preferably 800°C or higher. 300 more if necessary
It can be graphitized by heating to about 0°C.

Moreover, among the composites of the present invention, those with a relatively small ratio of menphase-containing pitch have a small volumetric shrinkage during carbonization, so instead of the two steps of pressure molding and carbonization, 800 to 3
It is also possible to form a carbon-based composite molded article in one step of pressure molding at 000° C. without causing any cracks.

In either method, it is possible to mix it with other Class 41 composites or to add other fillers as necessary during molding.

The key is to suspend the filler in a low-viscosity tar, recover the low-boiling fraction in the heat treatment process, and at the same time coat the filler surface with a highly sticky mesophase-containing pitch. Since the mesophase-containing pitch in the raw material for the molded body is sufficiently impregnated with the filler and has high adhesiveness, the raw material can be molded even when a small amount of about 5 to 30 parts by weight is used for 100 parts by weight of the filler. - By firing, a compact with practical strength can be obtained. This has great practical significance in that it reduces the volumetric shrinkage during carbonization and enables high-speed temperature rise without causing cracks.

When exposed to a larger amount of mesophase-containing pitch,
Features such as improved mechanical properties of the molded body can be obtained.

The method of the present invention is applicable to many types of fillers,
The obtained molded body raw material can be used in a wide range of applications. In addition, in the method of the present invention, since the production of mesophase-containing pitch and the recovery of low boiling point fractions are performed in the same process, filtration and
Another feature is that it does not require any accompanying processes such as extraction.

The present invention relates to a method for obtaining a graphite molded body with high electrical conductivity, high strength, and heat phosphoric acid resistance with almost no volume shrinkage or deformation during carbonization by pressure molding a mixed powder of mesophase-containing pitch and graphite. They filed a special application in 1984-1986.
A patent application has been filed under No. 9737. This method can be said to be an excellent technology in that it has established a technology that significantly suppresses shrinkage during carbonization, which was common knowledge in the conventional carbon industry, but there is still room for improvement in terms of the manufacturing process. That is, in order to obtain the molded body raw material powder by the method detailed in the examples of the application, the steps are: (1) Preparation of modified tar → (2) Production of modified pitch by distillation → (2) Heat treatment.

Production of mesophase-containing pitch by → ■ Grinding and mixing with graphite powder requires four steps. When the present invention is applied to this process, the number of steps can be significantly simplified: (1) Preparation of modified tar -> (2) Slurry of modified tar and graphite powder - Production of raw material powder by heat treatment9. Further, the raw material powder obtained by coating 100 parts by weight of graphite powder with 5 to 20 parts by weight of pitch according to this method has the advantage that it can be used as a molding raw material without requiring a pulverization process.

Carbine black has poor coal tar pitch tonneau kneading properties, and is car? When used with special carbon products such as carbon plastics, it was necessary for Kerr to provide a pretreatment process for Noblak to thoroughly treat the surface. In particular, carbon black with characteristics such as nobutyl phthalate oil absorption, large surface area, and low tag density, carbine black 1 weight t: h11
It is not possible to obtain a molded product unless a large amount of coal tar pitch of at least 5 parts or more is mixed with the carbon molded product.As a result, the properties expected by adding carbine black disappear. was not used as aggregate.

When the method of the present invention is applied, even bulky carbine black with an apparent specific gravity of 0.12 or less has carbon bluff 210.
A moldable raw material composite can be obtained by coating 10 to 500 parts of the 0 parts with pitch containing mesophase.

In addition, bulky carbine black (highly conductive carbine black manufactured by Mitsubishi Yuka Qing: HE-280P% HE320P,
When using Hg400P (trade name), etc., it is possible to carbonize the raw material composite obtained by the method of the present invention without causing deformation or cracking even if it is subjected to a 100~B reaction after pressure molding. discovered. Since the content of the menphase-containing pitch can be greatly changed, it has become possible to design molded bodies with various properties from porous to dense.

It was also found that the bending strength of the molded product was 880 ψ for a room temperature molded product carbonized at 1000° C., and that a high-strength product could be easily produced.

It can also be applied to composites with boron nitride and the like. For example, by coating 100 parts by weight of finely powdered silica alumina or γ-alumina with 10 to 500 parts by weight of mesophase-containing pitch, a raw material for an inorganic/carbon molded body having high strength and high hardness can be obtained. Similarly, a raw material for a high-strength carbon-inorganic composite can be obtained by coating 100 parts by weight of whisker-like silicon carbide with 30 to 100 inches of mesophase-containing pitch.

The method of the present invention is also effective for composites with metal powder. By further compounding graphite with the mesophase-containing pitchy carbine black system described above, it is possible to obtain a raw material for a molded body having high electrical conductivity even through low-temperature carbonization. On the other hand, a car for Pandagraph? For materials that require high strength and abrasion resistance, as well as high electrical conductivity, such as adhesive plates, it is possible to mix metals such as copper and scratches into high-strength carbon materials instead of graphite, which tends to wear out. Conventionally, efforts have been made to lower the specific resistance of the pickpocket plate.

By the method of the present invention in which a mixture of carbine black and copper fine powder of appropriate particle size is coated with mesophase-containing pitch, a composite in which carbon black, copper powder, and mesophase-containing pitch are uniformly dispersed is obtained, and the temperature is maintained at 1000 to 1500 °C.
By carbonization in , it is possible to obtain a molded body having both high strength and high electrical conductivity.

Further, by applying the method of the present invention, it is also possible to combine plating carmen and mesophase-containing pitch. For example, if carbine black is plated with copper or nickel and then coated with mesophase-containing pitch, a molded article can be obtained in which carbine black itself has high air conductivity.

Further, by mixing copper fine powder with the plated carmen and coating the mixture with mesophase-containing pitch, a molded body in which both the aggregate and the matrix portion have conductivity can be obtained. In addition, fl/iJ has also produced a carbon molded body with dramatically improved carbon conductivity by applying a powder containing a metal compound such as copper chloride by evaporation to dryness and coating it with mesophase-containing pitch. Obtainable.

When a metal is dispersed in a molded body using the method of the present invention, it is observed that the conductivity can be improved with a relatively small amount of metal addition compared to the conventional method of post-impregnation of molten metal into a molded body.

[Embodiments of the invention]

The content of the present invention will be explained in more detail below with reference to Examples and Comparative Examples.

Example 1 Naphtha decomposition residue tar generated by thermal decomposition of naphtha in an autoclave with an internal volume of 11 (normal pressure conversion point 170°C or higher)
629 and 30 silica alumina catalysts for fluid catalytic cracking (manufactured by Catalyst Kasei C@, alumina content 13%, powder), hydrogen was passed at 100 l/hour (STP), and the reaction pressure was 120 kg/err? The temperature was raised from room temperature to 460'C in 140 minutes while maintaining the temperature at 460'C, and maintained at that temperature for 80 minutes. After cooling to room temperature, the contents were taken out and the solid matter was filtered, and the modified naphtha decomposition residue tar 45
I got 5 no.

Equipped with an inner cylinder of IA 250 at containing scaly graphite (manufactured by Nippon Graphite Industries, trade name: CPB) 30, OF, which was degassed and dried at 150°C for 2 hours in a vacuum dryer, the distillate was poured into the pitch. The mixture was filled into a reactor completely protected from backflow, and 28.9 g of the modified tar and 29.9 g of quinoline (first class reagent) were added to form a slurry.

Argon is supplied to the bottom of the reactor inner cylinder at 1.751 per minute (STP).
,! , 2,3.4-tetrahydroquinoline was supplied in gaseous form at 0.75y per minute, and the reactor was immersed in a molten salt bath previously maintained at 493°C. After 11 minutes, the reaction temperature was 483°C.
After holding for 11 minutes, the mixture was cooled to room temperature to obtain a mixed powder of natural graphite and mesophase-containing pitch containing 16.4 severe scratches of mesophase-containing pitch. The quinoline-soluble fraction of the menphase-containing pitch contained in the mixed powder determined by the JIS-2425 centrifugation method is 22.8 times 4
It was 11%.

The mixed powder 1.70P is 63.5m long and 12.7m wide.
Fill into a true SUS mold and press at room temperature for 1 to 5 minutes.
TON//c11? (Guno) pressure? After applying pressure and performing a preliminary rJX type test, the temperature was raised to 13401: and held for 5 minutes while applying pressure. After cooling down to 200℃, the applied pressure is returned to normal pressure, the outer frame of the mold is opened, and after preventing the occurrence of stress cracks caused by the thermal shrinkage difference between graphite and mesophase-containing pitch and SUS, the product is cooled to room temperature. obtain the form,
100 at a heating rate of 5°C/min in an argon stream in a carbonization furnace.
The temperature was raised to 0°C, held for 30 minutes, and then cooled to room temperature to create a smooth surface with a length of 63.6 tnn, width of 12.9 ms, thickness of 1, Omvi, weight of k of 1.61 Ps, and apparent bulk density of 1. 84P74-1 Volume shrinkage rate based on the produced shape 0.3
A graphite molded body was obtained which had a weight reduction rate of 1.5 mm and a characteristic value of volume resistivity in the longitudinal direction of the plate by the four-terminal method of 1.3 mΩ.

The average bending strength in a three-point bending test of four graphite molded bodies obtained by the same method was 480 V-.

A polarized light microscopic observation was performed at room temperature on a sample obtained by embedding any part of the formed body obtained by the same method in an epoxy dome and polished, and it was confirmed that there were no places where the men7 process part existed as a large aggregate. did.

Example 2 Scale graphite 100 of Example 1. (1-) was packed into a reactor equipped with an inner cylinder having an internal volume of 11 to prevent backflow of the distillate into the pitch, and 247.65' of the naphtha cracking residue tar before reforming of Example 1 was added. While supplying nitrogen to the bottom of the inner cylinder of the reactor at a rate of 7.0 OJ per minute (STP), reaction a was immersed in a molten salt bath previously maintained at 483°C.After 36 minutes, the reaction temperature was 469°C. After reaching 21.7 weight f
A natural graphite-meso-7-containing pitch composite containing l14 was obtained. The quinoline soluble content in pitch containing menphase is 3
．． 7 layers 1il - I'm sorry.

After crushing the composite, it is equipped with a stress release mechanism and the diameter is 35.3.
tm (7) Filled into a SUS mold and heated to 1.5 TO
The temperature was raised to 350° C. while applying a pressure of N/i (5″-)) and then allowed to cool. After the temperature was lowered to 260° C., the pressure was released and the mixture was cooled to room temperature to obtain a formed body.

The formed body was carbonized in the same manner as in Example 1 to obtain a graphite shaped body. The molded body has a diameter of 35.3 m, a thickness of 1.0 m, a smooth surface, an apparent high density of 1.2%, a weight loss rate of 1.9 or more, and a volume resistivity of 1.0 m. OmΩ'ffi, bending strength 364'9/1yn2 and 7t.

Also, 1.5 TON/ltr at room temperature? The graphite molded body obtained by applying zero pressure for 10 minutes and carbonizing in the same manner has a diameter of 35.2 WrM, a thickness of 1.1, a bar reduction rate of 1.8, and a volume specific Resistance: 1.5 mΩ, mouth, strength: 239 ky/Crr? Deaffl.

Example 3 Scale graphite of Example 1 25. OP was charged into the reactor of Example 1, 64.31 liters of naphtha decomposition tar before reforming was added to make a slurry, and inversely, crab material was fed from the bottom of the vessel at 1.751 ml per minute.
While feeding, the reaction temperature was maintained at 425° C. for 5 hours, and cooled to obtain a composite of natural graphite-mesophase-containing pitch containing 18.8 weight percent of mesophase-containing pitch. The quinoline soluble content in the menphase-containing pitch was 5.9M.

The same aK as in Example 2 for the whole complex, 350°C, 1.5TON/
The graphite molded body obtained by carbonization after molding at cm' has a diameter of 3
5.3 ms, thickness 1.1 ml, smooth surface, apparent bulk density 1.85 P/l';;', volume shrinkage rate 4.4%, weight loss rate 1.8% based on the formed shape. , bending strength K
Example 4 30.0 l of scaly graphite from Example 1 was charged into the reactor of Example 1, and 369 g of naphtha decomposition tar before reforming and 1 quinoline were charged.
2.1! ＞'! In addition to this, make a slurry, and while supplying argon at 1.751/min from the bottom of the reactor, the reaction rate is 45% per minute.
The mixture was held at 0° C. for 30 minutes and cooled to obtain a composite of natural graphite and mesophase-containing pitch in which 10.4 layers of mesophase-containing pitch were engaged. The quinoline fat content in the menphase-containing pitch was 4.0%. The composite 1.71 was crushed and then filled into the same mold as in Example 1 [i-, i, s TON/cW. ? The temperature was raised to 420° C. while applying a pressure of (gauge) and held for 5 minutes. After the temperature was lowered to 250°C, the pressure was released for 7 seconds, and after cooling to room temperature, carbonization was performed in the same manner to obtain a graphite molded body. The molded body has a length of 63.9 m, (yellow 12.9 mm - thickness 1.1
rm flattened t[surface, volumetric shrinkage rate of 0.7% based on produced form, weight loss rate of 1.2%, volume b) resistance 0.
It had a bending strength of 8 mΩ"ffi and 400 kg/cry?.

Example 5 The scaly graphite of Example 1 was charged at 23.6 kg and P into the reactor of Example 1, and 75.5 kg of naphtha decomposition tar before reforming was added to form a slurry, and argon was blown at 1 min per minute from the bottom of the reactor. .7
1! While feeding, the mixture was held at 473° C. for 15 minutes and cooled to obtain a natural graphite-mesophase-containing pitch composite containing 24.3 kg of menphase-containing pitch. The amount of quinoline available in the menphase-containing pitch was 8.0. After crushing about 41 of the composite, it was packed into a graphite mold with an inner diameter of about 50+ m, and a pressure of 0.4 TON/cm2 (durso) was applied. Rabbit 11
While stirring, the temperature was raised to 1100° C. over 105 minutes and held for 5 minutes. After the temperature was lowered to 500° C., the pressure was released and the mixture was cooled to room temperature to obtain a graphite molded body.

The molded body has a diameter of 50.2 Bs and a thickness of 1. OB, bulk density 1.96, body fM lj in the plane direction by four terminal method VC!
・1 resistance 0.8 mΩ・m% bending strength 588 k, 9
It was 7α2.

Example 6 Modified tar of Example 1 59.97, technical college 71J, carbon black (Mitsubishi Yuka ■Wh product name HE-320P,
Nobutyl phthalate oil absorption path (JISK-6221 compliant)
320mJ/100PoN2 adsorption surface fil 700
m"15'. Volatile content 1.0%. Ash content 0.2%. Particle size 40 mμ. Apparent ratio NO, 12? / cc) 5, Of
F to the reaction tube of Example 1 & C to form a charging slurry.

Argon (in the warehouse shown in Example 1) and 1,2,3.4
- The reactor was immersed in a molten salt bath previously maintained at 495° C. while supplying tetrahydroquinoline to the bottom of the inner cylinder. 22
The reaction temperature reached 478°C after 11 minutes and was maintained at 1'i'J for 11 minutes.
A total of 13.95' of mixed mass of Kerr Plaque and Menphase Sprung Pitch containing 4.2M volume was obtained. The mixed mass was prepared at Hirako Seisakusho VIBRATING SAMPLE MIL.
The mixture was charged into a L size SAMPLE CHAMBER and ground for 5 minutes to obtain a mixed powder.

Approximately 11 of the mixed preparations were accurately weighed and placed in a 5 Qml Erlenmeyer flask with a stopper, 30 d't of warm quinoline was added, and the mixture was shaken at 80°C for 30 minutes using an ultrasonic shaker to dissolve the guinoline. A Whatman glass fiber filter paper (grade GF/D), which had been adjusted to a constant weight in advance, was poured into a Whatman 3-piece filter funnel kept at about 80°C, and the mixture was filtered under reduced pressure with a water jet pump. . The residue was then washed three times with 3 Qrnl of warm quinoline, and after cooling, washed twice with 30 d of acetone and air-dried with a stream of air. The residue and filter paper were dried under reduced pressure at 150°C for 1 hour to obtain a constant lid value, and the mesophase-containing pitch quinoline TIJi
¥1lit 51.6 positive! IL% was obtained.

When a part of the mixed mass was observed using a polarizing microscope using the method described in Example 1, a uniform distribution of menphase was observed.

1.05' of the mixed powder was charged into the mold of Example 1, and a pressure of 1.5 TON/crrI was applied at room temperature using a press machine to obtain a formed product, which was then placed in a carbonization furnace in an argon stream. 5
The temperature was raised to 1000°C at a heating rate of °C/min, held for 30 minutes, and then cooled to room temperature.Height: 62.0mm, Width: 12.6mm, Thickness: 1.1mm, Weight: 0.93p, Appearance Bulk density of 1.1
2? /cr11', body convergence rate l based on the generated form, 6
2. A carbonaceous molded body without swelling or distortion was obtained, which had an M content reduction rate of 7.17, and a characteristic value of volume resistivity in the plate length direction of 16.8 mΩ·ml by the four-probe method.

The average bending strength of two carbonaceous molded bodies obtained by the same method in a three-point bending test was 314 mm/cni''.

Further, 3.4 f f of the mixed powder was charged into the mold of Example 1, and 1.5 TON/c-rr? was formed using a press machine. After preforming by applying a pressure of The generation form standard. The carbonization reaction was carried out under the same conditions as in Example 6, except that the heating rate was 2.5° C./min. P
A carbonaceous molded body having characteristic values of 11.1 mΩ·a and a volume resistivity of 11.1 mΩ·a was obtained.

Three-point bending strength of two carbonaceous molded bodies obtained by the same method: 55
It was 5 ky/cm2.

Example 7 Using the same procedure as in Example 4, carbon black 2.0y and modified tar 47.9! i' was heat-treated at 480°C for 11 minutes to form pitch containing menphase (Kinori/soluble content: 33.
A composite 9.81 of carbon black and menphase-containing hitch in which 79.7 weights of double flt chips were engaged was obtained. Powder 1.01 obtained by pulverization using the method of Example 4 was molded and carbonized according to the procedure of Example 4 to form a powder with a length of 56.7 mm and a width of 11 mm.
．． 5m, thickness 0.96m, apparent bulk density 1.44f
/crn'', a formed J-toshi body with characteristic values of 24% volume shrinkage, 9.8% weight reduction rate, and 9.1 mΩ・α specific resistance based on the produced shape, and its average bending strength was 700 kf.
/crr? Met.

Example 8 Modified tar 7.51 of Example 1, SI manufactured by Tokai Carbon ■
Example 1 of C whisker (talkermax) 2.55'
The mixed granules were heat-treated in a reactor and under the following reaction conditions to obtain mixed granules having a menphase-containing pitch content of 31.4% by weight. The amount of quinoline soluble content determined by the method of Example 1 was 5
5.3% by weight. The mixed granules were pulverized by the method of Example 6, charged into the mold of Example 1 with 3.56 p'i, and molded and carbonized by the procedure of Example 7 to give a length of 63.
4 dragons, width 12.8 chickens, thickness 2.2cm, apparent density 1.
92 P/cm", bending strength 700 ky/cn12
A molded body with characteristic values of was obtained.

Example 9 Highly conductive carbon black (HE-320P) of Example 6
)55', cupric chloride dihydrate salt 2.01fi'fr3
In a 00ml eggplant-shaped flask, add 140d of methanol.
was added to dissolve the cupric chloride to completely form a slurry, the temethanol was distilled off using a rotary evaporator, and the slurry was further dried at 100° C. under reduced pressure in a reduced pressure drying vessel for 2 hours. The composition 5,
01 was added with 59.75' of the modified tar of Example 1, heat-embedded according to the procedure of Example 1, and the content of menphase-containing pitch was 67.1 polymerization ratio, measured by the method of Example 6. Mixed mass 1 with a quinoline soluble content of 45.2M
5.25'f was obtained, and it was crushed, molded, and carbonized by the method of Example 6, and the length was 58.1 ttm, the width was 11.7 mm, and the thickness was 3.5 mm.
8 mrx, apparent density 1.46f/'tyn', specific resistance 7.6 mΩ・σ, bending strength 455ky/cm'
A molded body with the following characteristics was obtained.

Comparative Example 1 The reformed tar was distilled using the method of Example 1, and the fraction below 490° C. in terms of normal pressure was removed to obtain hydrogen-treated pitch at a yield of 25 mft% based on the charged raw materials. The modified pitch 105' obtained as described above was placed in a reactor equipped with an inner cylinder having an internal volume of 40 ml to prevent backflow of distillate into the pitch, and argon was introduced at a rate of 0.351, 1. 2,3.4-tetrahydroquinoline was fed completely in liquid form at a rate of 0.1354 pitches per minute and held for 10 minutes. After that, the temperature was maintained at 485°C in advance and the solution was fed steadily, and heat treated at a reaction temperature of 483°C for 13 minutes. 〇 Menphase-containing pitch was obtained with a yield of 53% by weight for the hydrogen-treated pitch, the quinoline soluble content was 53% by weight, and the menphase content was approximately 100%. Carbon of Example 6 Mix all of the menphase-containing pitch 5 in Black 11, grind and mix for 10 minutes in the vibrating mill of Example 2, and charge the mixture 4y- into the mold of Example 1,
After preforming with a press machine (with a press of 1.5 TON/err?), the mold temperature was raised to 340°C under an applied pressure of 0, 5 TON/cWI2, held for 5 minutes, cooled to 200°C, and the applied pressure and mold The outer frame was opened and cooled to room temperature.The resulting product was brittle, and there were many places where carbon black remained as small lumps, and the small lumps were easily broken off by simply applying a small external force.

〔Effect of the invention〕

The effects of the present invention can be summarized as follows.

(1) A raw material for a carbon-based composite molded body having a dotted line with menphase-containing pitch and high total adhesiveness on the filler surface is obtained.

(2) High-strength molded product even with a small ratio of menphase-containing pitch to filler? Obtainable.

(3) By selecting the ratio of menphase-containing pitch and the molding conditions, the properties of the molded product can be varied widely.

(4) The process is simpler than conventional methods.

(5) A complete carbon composite molded body of amorphous compounds can be produced.

(6) Metal components can be easily composited.

(7) New molded objects can be created by bringing out the functions of bulky materials.

Claims (1)

[Claims] 1. Production of a raw material for a carbon-based composite molded body comprising one or more materials selected from graphitic carbon, carbonaceous carbon, inorganic compounds, metals, and metal compounds and mesophase-containing pitch. In the method, (1) suspending one or more materials selected from graphitic carbon, carbonaceous carbon, inorganic compounds, metals and metal compounds in a tar fraction containing a mesophase pitch precursor; (2) The suspension system is heated, the light fraction contained in the tar fraction is distilled off by blowing inert gas or vacuum suction, and the mesophase pitch precursor is heat-treated at 350 to 520°C. A method for producing a raw material for a carbon-based composite molded body, characterized by using two steps: obtaining a carbonaceous precursor in which mesophase-containing pitch containing 2 to 90% of quinoline soluble content is produced on the surface of the material. .