JPS61136906A - Production of carbon series composite molded body - Google Patents

Abstract

PURPOSE:To obtain the titled molded body excellent in strength, dimensional stability and low electrical resistivity by distilling the more volatile fraction of distillate contained in the tar fraction contg. the mesophase pitch precursor which is suspended with the specified material, carbonizing or graphitizing it after molding. CONSTITUTION:After 5-1,000pts.wt. one or >=2 kinds of material selected among graphitic carbon, carbonaceous carbon, an inorganic compd. and metal (compd.) are suspended into 100pts.wt. tar fraction contg. a mesophase pitch precursor and an inert gas is blown thereinto to distill the more volatile fraction of distillate, it is heated at 350-500 deg.C to obtain the carbonaceous precursor wherein the mesophase-contg. pitch contg. 5-90wt% quinoline soluble content is formed on the surface of material. Then the precursor is molded at the temp. <=400 deg.C from the softening temp. and above the S.P. of pitch and the obtained green molded body contg. mesophase pitch-contg. pitch is carbonized or graphitized in the temp.-rise velocity of 1-1,500 deg.C/hr in an inert atmosphere.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention provides a mesophase-containing pitch using 1fa or two or more materials selected from graphitic carbon, carbonaceous carbon, inorganic compounds, metals, and metal compounds. The present invention relates to a method for manufacturing a carbon-based composite molded body coated with carbonaceous or graphite derived from carbonaceous materials.

[Prior art]

Generally, when manufacturing carbon materials such as graphite electrodes, 100 parts by weight of aggregate is added to aggregate such as coke, which does not have caking properties by itself and cannot be used to form a press-molded product. A widely used method is to add 30 to 40 parts of pitch as a binder, and to perform the steps of cross-wiring, 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 carbonization rate of the pitch 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, Japanese Patent Application Laid-Open No. 52-2421.1 describes an improved technique for mixing aggregate and binder pitch.

The publication states that carbonaceous or graphite powder is mixed with pitch, this mixture is heated at 350 to 450°C, and the mesophase produced from the pitch is added to 1 part by weight of carbonaceous or graphite. A method for producing a carbonaceous compact, which involves separating the carbonaceous or graphite powder and mesophase from the pitch, press-molding it as it is, and firing it. , or during heat treatment of the pitches, the carbonaceous or graphitic material and mesophase obtained after the heat treatment so that almost the entire amount of the pitches transfers to mesophase are crushed, then pressure-formed as they are, and fired. A method for manufacturing a carbon molded body made of carbon or graphite to which mesophase is attached is disclosed.

The characteristics of this method are as follows: (1) Since Men7Aze adheres around the additive, no kneading step is required.

(1υ Since the carbonization yield of the mesophase is high and it does not pass through a softened and molten state during carbonization, it is possible to achieve a temperature increase rate of Zoo℃/hr or more.

(The mesophase generated in the 110 pitch penetrates into small gaps in the carbonaceous and graphite materials, so the porosity of the carbonaceous and graphite materials themselves does not affect the carbonized compact.

etc. are listed.

In addition, in Japanese Patent Publication No. 5g-39770, carbonaceous aggregate,
Carbonaceous molding characterized in that solid matter is separated by T-filtering all or part of the liquid medium soluble content from a slurry consisting of a liquid medium containing bituminous material, and this solid matter is subjected to heat treatment after pressure molding. A method of manufacturing a body is disclosed. The aggregate used may be various types of coke, natural graphite, artificial graphite, carbon black, carbon fiber, etc., and preferably contains at least half of the powder that can pass through a 200 micron sieve. The bituminous materials used as binders include coal tar, coal tar pitch, petroleum pitch, 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. It is characterized by using a product from which all or a part 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. Using this method, it is easier to uniformly disperse the effective adhesive components in the bituminous material into the fine powder. When using ultrafine powders such as carbon black, the conventional method involves dispersing the caking components on the surface of the carbon black.

However, the method of the present invention has advantages such as simultaneous immersion. Also, conventionally 3 to 6
This process, which takes several months, can be shortened to 7 to 10 days by using this method, which also allows direct graphitization, and the harmful dust and mist generated in conventional processes such as kneading, cooling, and secondary grinding can be removed using organic media. It has also been shown that there are advantages such as the ability to maintain a good working environment because it can be dissolved and removed.

Furthermore, the present inventors have disclosed in Japanese Patent Application Laid-Open No. 52-24211,
Among the graphite substances that are said to be unable to form pressurized bodies as they are, we focused on the fact that some graphites can form pressurized bodies under pressure, and carbonized this graphite at 400°C and 100°C. A powder obtained by mixing with mesophase-containing pitch powder with a yield of at least 70 weight tS is press-molded to obtain a green body, and the green body is further fired at 700°C or higher in an inert atmosphere. This paper proposes a method for producing a molded body with a volume resistivity of 5 ohms or less, a bending strength of Zooky/- or more, a volume change before and after firing of 3% or less, and a weight change of 3% or less. (Japanese Patent Application No. 59-199737) 0 The graphite molded body obtained by this method has been shown to be suitable for uses such as cell members of pyrochloric acid fuel cells.

[Problem that the invention seeks to solve]

The mesophase obtained by the method described in JP-A-52-2.4211 essentially enables high-speed carbonization that could not be achieved with conventional binder pitches using quinoline solvents; Text (carbon, 86, P93 (
1976)), the porosity of the carbonaceous molded body obtained by the method of the invention is about 15-30%, and the bending strength is about 120-5ookf/- when fired at 1000°C. That is, since the mesophase does not melt and soften, it is impossible to produce an essentially dense molded product.Also, since the amount of binding components is originally small, when the mesophase content decreases, the strength decreases significantly, and in this method, the strength decreases significantly. It has been shown that approximately 65 inches of mesophase is required to obtain a flexural strength of cli. In addition, if it is necessary to separate a large amount of pitch with an organic solvent such as quinoline after mesophase generation, the separated mesophase and coke need to be washed with benzene and acetone and then subjected to a vacuum drying process. However, from a process perspective, a complicated processing step is required in place of the crosstalk step. In addition, when all pitch is converted to mesophase, I/C seems to have a solid phase problem, such as controlling the amount of meta-7Aze that does not have caking properties.

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-resin. 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. 199737/1980 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
Its purpose is to consist of one material selected from graphitic carbon, carbonaceous carbon, inorganic compounds, metals and metal compounds, or a material of 2m or more, and carbonaceous or graphite derived from mesophase-containing pitch. , high strength, fast carbonization,
An object of the present invention is to provide a method for manufacturing a carbon-based composite molded body having excellent dimensional stability and low electrical resistance.

(Structure of the Invention) That is, the present invention provides: 1. One or more materials selected from graphitic carbon, carbonaceous carbon, inorganic compounds, metals, and metal compounds and carbonaceous or graphite derived from mesophase-containing pitch. (1) One or more materials selected from graphitic carbon, carbonaceous carbon, inorganic compounds, metals, and metal compounds are mixed with a mesophase pitch precursor. The process of suspending in a tar fraction containing.

(2) The suspension system is heated and the light fraction contained in the tar fraction is heat-treated by blowing inert gas to produce the menphase-containing pitch containing 5 to 90% of quinoline soluble content. A process of obtaining a carbonaceous precursor formed on the surface.

(3) A step of molding the returned elemental material precursor into a formed body containing mesophase-containing pitch.

(4) A step of subjecting the formed body to a carbonization or graphitization reaction under an inert atmosphere to contain carbonaceous or graphite derived from the mesophase-containing pinch.

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

(Detailed Description of the Invention) (1) Step of making the material cloudy with tar fraction Vcs The material from which the mesophase-containing pitch used in the present invention is to be precipitated (
Hereinafter, it may be abbreviated as "filler". ) 0 Examples of the graphitic carbon powder include scaly natural graphite, earthy natural graphite, and artificial graphite 0 Furthermore, in order to make the method of the present invention more effective, pressure molding at room temperature can be used. Graphite powder that can form a molded body (for example, CPB and A8P-10,00 (Ii product name) manufactured by Nippon Graphite Industries ■?LO
Examples of the carbonaceous carbon powder include petroleum coke, coal coke, and carbon black. Examples of the inorganic compound powder include: Examples include silica-alumina, r-alumina, a-alumina, silicon carbide, and silicon nitride. Examples of the metal powder include iron, copper, zinc, tin, nickel, cobalt, lead, aluminum, gold, silver, titanium, platinum, and palladium. Part or all of these metal powders may be present as metal oxide powders or metal compounds up to the stage of slurrying and the stage of containing them in a formed form. Further, as a metal compound, for example, Few O
x, ZnO1CuO1CuC12, ZnC1z, Zen-a
il 8nC1a, AI C1s, TiCl4, Cu
(NOs)z, etc. can be mentioned.

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 more than one species can also be used.

Specific examples of mixed systems of two or more types include combinations of graphite and carbon, carbon and inorganic compounds, carbon and metals, and the like. Furthermore, examples of filler combinations include carbon powder that has been plated in advance 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 mesophase-containing pitch containing 5 to 90% by weight of quinoline solubles under operable reaction conditions can be used; however, depending on the properties required for the final product, Seeds may also be selected. 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 heavy component tar of petroleum.

In addition, if the material has a large oil absorption and a slurry cannot be formed even if you try to suspend it only in the tar fraction containing the mesophase pitch precursor, use an appropriate solvent, for example, in the tar fraction recovered in the heat treatment process. A light distillate, quinoline, etc. can also be added as appropriate.

In addition, the amount of filler to tar fraction is preferably 5 to 1000 parts by weight per 100 parts by weight of tar fraction, although the preferable blending amount varies depending on the type of tar fraction and filler.
The amount is preferably 10 to 800 parts by weight.

For suspension, a normal method is used, but if the tar fraction contains a large amount of moisture that may prevent the filler surface from being completely infiltrated, it is preferable to dry and degas it in advance. .

Furthermore, if the difference in specific gravity between the tar fraction and the filler is large, it is desirable to avoid separating the two components.

(2) Production process of meso-7Aze pitch on the surface of the material The mesophase-containing pitch that meets the requirements of the present invention is produced by heating a slurry consisting of a tar fraction and a filler at 350 to soo°C.
Preferably, the slurry produced by heat treatment in the reaction range of 400 to soo C is heated under a flow of an inert gas such as nitrogen gas, carbon dioxide, or argon, or for example, 10=1005 m
The temperature is raised to the reaction temperature under reduced pressure of Hf, maintained for a predetermined time, and then cooled to obtain a composite of filler and mesophase-containing pitch. Meng contained in the tar fraction during the heating process.
The so-called light fractions, such as the fractions that do not become the Zubitsu precursor and, if necessary, organic solvents, are distilled out from the reaction system and are recovered by an appropriate method.

The temperature increase rate should be 1 to b. After reaching the reaction temperature, it is necessary to maintain the temperature for a time when the quinoline soluble content of the mesophase-containing pitch reaches the target value.
This retention time is closely related to various factors such as reaction temperature, temperature increase rate, gas flow rate or degree of pressure reduction, filler material, type of tar fraction, amount of quinoline solubles, and whether or not a hydrogen donor is injected into the reaction system. There is an interdependent relationship between the materials constituting the present invention and their combinations (therefore, each must be determined experimentally. Specific examples can be shown in the Examples). In order to facilitate control of the reaction, a compound having hydrogen donating ability is blown into the reaction system together with an inert gas using the method disclosed in JP-A-59-155493, and furthermore, JP-A-58-154
No. 792, Publication No. 58-154793 and Japanese Patent Application No. 1983-
No. 35563, No. 59-97183 and No. 59-9718
As disclosed in No. 4, the tar fraction can be reformed in the presence of pressurized hydrogen or in the coexistence of pressurized hydrogen and a catalyst, and then used as the material of the present invention. In addition, if the difference in specific gravity between the mesophase-containing pitch and the filler is large, uniform precipitation can be achieved by mechanically stirring the reactant or fluidizing it by blowing inert gas in order to avoid separation of surrounding components. .

Quinoline soluble content of mesophase-containing pitch is 5 to 90
% by weight, preferably 20-70% by weight. If the amount of quinoline soluble content is too small, there will be too little viscous component during room temperature molding, making it impossible to obtain strength in both the formed body and the carbonized body, and during hot molding, the mesophase-containing pitch may melt at temperatures below 400°C. This is not preferable because it becomes impossible to obtain a dense carbonized molded body. On the other hand, a colander containing a large amount of quinoline solubles is not preferable because gas generation during carbonization is significant and bubble formation and deformation occur during carbonization.

Note that the heat treatment temperature of the meso-7 pitch precursor was 350 °C.
When the temperature is lower than 0.degree. C., it takes a long time to form a mesophase, which is undesirable from the viewpoint of processing and controlling the amount of soluble quinoline. Furthermore, when the temperature is higher than 500°C, higher-order polymerization of the quinolinated component is promoted, and the quinolinated component with properties similar to coke exists, resulting in a mesophase-containing pitch suitable for hot melt molding as the object of the present invention. ) is not desirable.

Quinoline soluble content can be measured using #1JIs-2425 centrifugation method, but in the case of a composite with a fine filler such as carbon black, carbon black does not settle even after centrifugation, so it is removed as quinoline soluble content, causing an error. Therefore, the following method was used to completely capture the fine particles and measure the amount of quinoline solubles.

Accurately weigh approximately 100 meshes or less of a composite of pulverized mesophase-containing pitch and carbon black (the abundance ratio of both is calculated from the weight balance before and after the heat treatment reaction) using a vibration mill, and place it in a 50 m Erlenmeyer flask with a stopper. put in,
Add 30-g of warm quinoline to this, stopper it, and heat it to 80°C for 30-30 min.
A glass fiber filter paper with a permeation particle size of 2.7 mm, which had been subjected to ultrasonic vibration for 1 minute to dissolve the quinoline soluble matter and had a constant weight in advance, was attached to a Whatman 3-piece filter funnel. The slurry in which quinoline had been dissolved was kept at 80° C., and the quinoline-soluble content was filtered out under reduced pressure with a water jet pump.

Then wash the residue on the filter paper three times with warm quinoline 30-
After washing with 77 tons and 30 liters at room temperature, it was air-dried with an air stream, and the filter and paper were dried to a constant weight at 150° C. in a vacuum dryer to determine the amount of residue. The quinoline soluble content (% by weight) t was calculated from the amount of mesophase-containing pitch contained in 1 ton of composite.

(3) Molding process of carbonaceous precursor The composite obtained by the method of the present invention can be made into a green body by pressure molding. The molding temperature can be arbitrarily selected from room temperature to a temperature at which the mesophase-containing pitch does not undergo thermal decomposition. Generally, when you want to obtain a porous body, molding is performed at a temperature below the softening point of the mesophase-containing pitch, and when you want to obtain a dense molded body, it is molded at a temperature above the softening point of the mesophase-containing pitch.
It can be molded at temperatures below 00°C (substantially 200 to 400°C).

(4) Graphitization step for carbonization of compacts The compacts obtained by the method of the present invention are
The carbonization and graphitization reactions can be carried out at a heating rate of b 00°C/hour, more preferably 50 to SOO°C/hour. Deformation due to its own weight can be prevented by placing the large plate-like body on a carbonaceous plate or by sandwiching it and subjecting it to the carbonization reaction. By setting the carbonization temperature to 700° C. or higher, preferably 800° C. or higher, the carbon-based composite molded article that is the object of the present invention can be obtained. The graphitization reaction is carried out under an inert atmosphere.
Depending on the purpose, it can be carried out at a heating rate of 5 to 100°C/hour up to about 3000°C.

(Features and application examples of the method of the present invention) By press-molding a mixed powder of mesophase-containing pitch and graphite, high conductivity, high strength, and heat resistance with almost no volume shrinkage or deformation during carbonization can be achieved. The present inventors have disclosed a method for obtaining a graphite molded body with
A patent application has been filed under No. 9737. This method can be said to be an excellent technology in that it establishes a technology that significantly suppresses carbon death shrinkage, which was common knowledge in the conventional carbon industry, but it is wasteful in terms of the manufacturing process. That is, as detailed in the examples of the application, in order to obtain the raw material powder for the molded body, the steps are: ■ Preparation of i-cool → ■ Production of modified pitch by distillation → ■ Production of mesophase-containing pitch by heat treatment → ■ Combination with graphite powder It requires a long process of grinding and mixing. Applying the present invention to this process:
■ Preparation of metamorphic tar → ■ Production of raw material powder by heat release of slurry of metamorphic tar and graphite powder, and the number of steps can be significantly simplified. The content of mesophase-containing pitch is 5 to 50 parts by weight based on 100 parts by weight of graphite powder,
Preferably, in the range of 10 to 40 parts by weight, the composite powder of graphite and mesophase-containing pitch does not cause mutual fusion, so there is no need for a pulverization process at all, and the advantage is that it can be charged into a mold for pressure molding. have

By applying a hot press molding method to the composite of mesophase-containing pitch and various fillers obtained by the method of the present invention, it is possible to make the molded product denser and significantly improve its strength.

Carbon black has poor cross-talk with coal tar pitch, and when used in special carbon products such as carbon brushes, it is necessary to perform a carbon black pretreatment step to thoroughly treat the surface. However, with carbon black, which has the characteristics of high dibutyl phthalate oil absorption, high surface area, and low tap density, a molded product cannot be obtained unless a large amount of coal tar pitch is mixed in at least 5 parts by weight per 1 part by weight of carbon black. As a result,
Since the properties expected by adding carbon black disappear, as a result, even though it possesses desirable properties such as high electrical conductivity, it has not been used as an aggregate for carbon molded bodies.

When the method of the present invention is applied, the apparent specific gravity is 0.12t7c
Even if the carbon black is bulky as below, a formed body with homogeneous properties can be obtained by room temperature molding and heat molding by allowing 0.1 to 5x parts of mesophagous-containing pitch to be present per 1 part by weight of carbon black. be able to.

Also, surprisingly, bulky carbon black (
Mitsubishi Yuka Highly conductive carbon black; HB-280
PSHB320P, HE400P (product name), etc.), such a formed body can be deformed or cracked even if it is subjected to a carbonization reaction at a speed that cannot be expected from the technology for producing a 100~B bomb black molded body. It was discovered that carbonization is possible without any carbonization.

Since the content of mesophase-containing pitch can be greatly varied, it has become possible to design molded bodies with various properties ranging from porous to dense.

In addition, it was found that the bending strength of the molded product was 880 kp/- for a room temperature molded product carbonized at 1000° C., and that a high-strength product could be easily manufactured.

The method of the present invention can also be applied to silica alumina, r-alumina, α
- It can also be applied to composites with alumina, carbon silicon, silicon nitride, boron nitride, etc.

For example, by precipitating 10 to 10 parts by weight of mesophase-containing pitch per 100 parts by weight of fine powdered silica alumina or r-alumina, press-forming it, and then carbonizing it, high strength and high hardness can be achieved. An inorganic/carbon molded body can be obtained.

30 to 100 parts by weight of whisker-like silicon carbide
By adding parts by weight of menphase-containing pitch, a high-strength carbon-inorganic composite can be obtained by firing at 1000 to 2000°C.

In the method of the present invention, a molded article can be obtained with at least the amount of menphase pitch as a binder for the inorganic compound.
There is little deformation during the carbonization process, and the temperature increase rate can be relatively high.

The method of the present invention is also effective for composites with metal powder. If graphite is further combined with the mesophase-containing pitch-carbon black system described above, a molded article having high electrical conductivity can be obtained even by low-temperature carbonization. On the other hand, for materials that require high strength and abrasion resistance, as well as high electrical conductivity, such as carbon slip plates for Pandagraphs, metals such as steel and tin are used instead of graphite, which tends to wear easily. Conventionally, efforts have been made to lower the specific resistance of pickpockets by blending them with high-strength carbon materials.

By the method of the present invention, which precipitates mesophase-containing pitch from a mixture of carbon black and fine copper powder with an appropriate particle size, a composite in which carbon black, copper powder, and mesophase-containing pitch are uniformly dispersed can be obtained.
By carbonizing at 0°C, it is possible to obtain a molded body with both high strength and high electrical conductivity. Furthermore, by applying the method of the present invention, it is also possible to combine plated carbon and mesophase-containing pitch. . For example, by plating carbon black with steel or nickel and then precipitating mesophase-containing pitch, it is possible to obtain a molded body in which the carbon black itself has high electrical conductivity. Further, by mixing copper fine powder with plated carbon and precipitating mesophase-containing pitch, it is possible to obtain a molded body in which both the aggregate and the matrix portion have conductivity. A carbon molded body with dramatically improved conductivity can also be obtained by depositing mesophase-containing pitch on a powder prepared by carrying a metal compound such as chlorinated steel on carbon black by evaporation to dryness.

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 the addition of a relatively small amount of metal 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 Soot decomposition residue tar produced by thermal decomposition of soot in an autoclave with an internal volume of 11 (normal pressure equivalent boiling point 170°C or higher)
6299 and silica alumina catalyst for fluid catalytic cracking (manufactured by Catalyst Kasei, alumina content 13% by weight, powder) 301Ff
t preparation, hydrogen every hour.

1 (8 TP), the temperature was raised from room temperature to 460 °C-1 in 140 minutes while maintaining the reaction pressure at tzokr/cd (gauge), and the contents were evacuated after cooling to 0 occlusion temperature, which was maintained at VC for 80 minutes. The solid matter was filtered to obtain 455 tons of modified soot decomposition residue tar.

Scaled graphite (
Nippon Graphite Industries ■, trade name CPB) 30゜at was charged into a reactor equipped with an internal volume 25G-〇 inner cylinder to prevent backflow of the distillate into the pitch, and the modified tar 28.9 f
and 29.92 liters of quinoline (test grade 1) were added to form a slurry. Argon is supplied to the bottom of the reactor inner cylinder at a rate of 1.75 per minute.
1(8Tf'), 1,2°3.4-tetrahydroquinoline in gaseous form at 0.75?/min. 493 in advance while supplying
The reactor was immersed in a molten salt bath maintained at °C. After 11 minutes, a temperature of 483° C. was obtained in the reactor, which was maintained for 11 minutes and then cooled to room temperature to obtain a mixed powder of natural graphite and mesophase-containing pitch containing 16.4% by weight of mesophase-containing pitch. The amount of quinoline soluble content in the Men7Aze-containing pitch contained in the mixed powder determined by the JIS-2425 centrifugation method is 2.
It was a 2.8 weight attack.

1.7 of the mixed powder was filled into a SUS mold with a length of 63.5 mm and a width of 12.7 mm, and was heated to 1.5 T at room temperature using a press machine.
After preforming was performed by applying a pressure of 'ON/cj (gauge), the temperature was raised to 340° C. and held for 5 minutes while the pressure was being applied. After cooling down to 200°C, the applied pressure was returned to normal pressure, the outer frame of the mold was opened, and the graphite and mesophase-containing pitch and SO
After preventing the occurrence of stress cracks caused by the difference in thermal shrinkage in step 2, the product was cooled to room temperature to obtain a green body, and then heated to 1000°C at a heating rate of 5°C/min in an argon stream in a carbonization furnace.
After holding for 0 minutes, cool to room temperature and make a vertical 6 with a smooth surface.
3.6 Cod, Width 12#9 Kasumi, Thickness 1.0 Cod, Weight 1.61
f, apparent high density g 1.84/l:j, volume shrinkage rate based on the formed shape 0.3%, weight reduction rate 1.5 inches, volume resistivity in the plate length direction by four-terminal method 1.3 tmΩ・A graphite compact with a characteristic value of α was obtained.

The average bending strength in a three-point bending test of four graphite molded bodies obtained by the same method was 480 kp/aII. A sample in which any part of the formed body obtained by the same method was embedded in epoxy resin and polished. We conducted polarized light microscopy observations at room temperature and confirmed that there were no locations where mesophase portions existed as large aggregates.

Example 2 Modified tar 59.9f of Example 1, highly conductive carbon black (trade name HE-az manufactured by Mitsubishi Yuka Corporation).

P0 diptylphthalate oil absorption (according to JISK-6221) 320 d7100 P oN* Adsorption surface area 7
00td/f0 Volatile content 1.0%0 Ash content 0.2'%o Particle size 40111j, apparent specific gravity 0.12 f/CC)
5. Of argon (in the amounts shown in Example 11C) and 1,2 were charged to the reaction tube of Example 1 to form a slurry.
, 3.4-tetrahydroquinoline was supplied to the bottom of the inner cylinder while the reactor was immersed in a molten salt bath previously maintained at 495°C. After 22 minutes, the reaction temperature reached 478°C, and after holding for 11 minutes, it was cooled to room temperature, and the mesophase-containing pitch reached 6
13.9 f of a mixed mass of carbon black and mesophase-containing pitch containing 4.2% by weight was obtained. The mixed mass was prepared using VIBRATING SAMPLE M manufactured by Hirako Seisakusho.
The mixture was charged into a SAMPLE CHAMBER for ILL and ground for 5 minutes to obtain a mixed powder.

Approximately 11 parts of the mixed powder was accurately weighed and placed in a 50-conjugated Erlenmeyer flask, 30 parts of warm quinoline was added thereto, and the mixture was shaken at 80°C for 30 minutes using an ultrasonic shaker to dissolve the quinoline. Whatman glass fiber filter paper (grade GP/D), which had been made to a constant weight in advance, was dissolved and the
The mixture was poured into a Whatman 3-piece filter 7 anel kept at 0° C. and filtered under water pump vacuum. Then, the residue was washed three times with warm quinoline 30-3, and after cooling, acetone 3-3
The 0 residue and filter paper, which were washed twice with 0- and air-dried with a stream of air, were dried under reduced pressure at 150 °C for 1 hour in vacuum drying 6 to obtain a constant weight value, and the quinoline-soluble content of the mesophase-containing pitch was 51.6% by weight. Ta.

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

The mixed powder 1. Of - The mold of Example 1 was charged, a pressure of 1.5 TON/- was applied at room temperature using a press machine to obtain a formed body, and the temperature was increased at a heating rate of 5°C/min in an argon stream in a carbonization furnace. The temperature was raised to 100°C, held for 30 minutes, and then cooled to room temperature.Length: 62.01wI, Width: 12.6cm, Thickness: 1.1cm
■, weight 0.93f, apparent bulk density 1.12f/
cj, carbon with no swelling or distortion, with a volume shrinkage rate of 1.62 cm based on the formed shape, a weight reduction rate of 7.17%, and a characteristic value of volume resistivity in the plate length direction of 16.811Ω・α by the four-terminal method. A quality molded body was obtained.

The average bending strength of two carbonaceous molded bodies obtained by the same method in a three-point bending test was 314 kf/c'j.
- Example 3 Carbon black 2. Of and 47.9 t of modified tar were heat treated at 480°C for 11 minutes,
9.8 tons of a composite of carbon black and mesophase-containing pitch containing 79.7% by weight of mesophase-containing pitch (quinoline soluble content: 33.2% by weight) was obtained. Powder obtained by pulverization using the method of Example 20 1. It was molded and carbonized according to the procedure of Off Example 2, and had a length of 56.7 m, a width of 11.5 cm, a thickness of 0.96 m, an apparent bulk density of 1.44 f/ad, and a volume shrinkage rate of 24% based on the formed body. Weight reduction rate 9.8%,
A molded body with a characteristic value of resistivity of 9.1 mΩ was obtained,
The average bending strength was 700 kf/cII. Example 4 Mesophase-containing pitch-carbon black mixed powder of Example 2 3° 4ft was charged into the mold of Example 1 and pressed to 1.5 TON/- After preforming by applying a pressure of The resulting shape was obtained. The carbonization reaction was carried out under the same conditions as in Example 2 except that the heating rate was 2.5°C/min.
．． A carbonaceous molded body was obtained having a thickness of 3.3 mm, an apparent density of 1.32 P/j, and a volume resistivity of 1.1.1 ItΩ.

Three-point bending can made of two carbonaceous molded bodies obtained by the same method The strength was @ss kg/cd.

Example 5 Modified tar of Example 1 7.5? , Tokai Carbon 8i
E-whisker (Tokamax) 2.5 F was heat-treated in the reactor and reaction conditions of Example 1 to produce mixed granules 366f with a mesophase-containing pitch content of 31.4% by weight.
I got it. The quinoline soluble content determined by the method of Example 1 was 55.3% by weight. The mixed granules were pulverized by the method of Example 2, 1.3.56 f was charged into the mold of Example 1, and molded and carbonized according to the procedure of Example 30.
A molded body was obtained with characteristic values of 3.4 mm, width 12°8 s*, thickness 2.2 mm, apparent density 1.92 t/j, and bending strength 700 kg/-.Example 6 The height of Example 2 Conductive carbon black (HE-320P
) 5t, chlorinated steel II/dihydrate salt 2.01f 300-
9, 1401 g of methanol was added to the Nasuya flask and the secondary steel chloride was dissolved to form a slurry IJ-.The methanol was distilled off using a rotary evaporator, and the mixture was further dried at 100° C. under reduced pressure in a vacuum dryer for 2 hours. The composition 5. O
59.7 f of the modified tar of Example 1 was added to f and heat treated according to the procedure of Example 1, and the content of mesophase-containing pitch was 67.1% by weight, which was determined by the method of Example 2. Mixed mass 15 with a dissolved content of 45.2% by weight
．． 21 was obtained, which was crushed, molded, and carbonized by the method of Example 2, and was made to have a length of 58.1 m and a width of 11.2 m. Lw, thickness 3.8■, apparent density 1.46 y/clI, specific resistance 7.6 wtΩ
Obtain a molded product with φ and bending strength of 455 kq/do.

Comparative Example 1 The reformed tar obtained by the method of Example 1 was distilled to a standard pressure equivalent of 49
Excluding the fraction below 0°C, hydrogen-treated pitch was obtained at a yield of 2.5% based on the charged raw materials. The reformed pitch 10F obtained in the above manner was placed in a reactor equipped with an inner cylinder having an internal volume of 40 mm to prevent backflow of distillate into the pitch, and argon was introduced at a rate of 0.357.1°2 per minute. .3.1 while feeding 4-tetrahydroquinoline in liquid form at a pitch of 0.13 f/min.
After holding for 0 minutes, it was immersed in a molten salt bath kept at 485°C.

After the pitch has melted, argon and tetrahydroquinoline are fed into the liquid pitch, and the reaction temperature is 483°C.
Heat treated at ℃ for 13 minutes 〇 53% for hydrogen treated pitch
Pitch containing Men7Aze was obtained with a yield of 10% by weight, a quinoline soluble content of 53% by weight, and a mesophase content of 10% by weight.
It was 0chi.

The mesophase-containing pinch 5? is added to the carbon black 1f of Example 2? The mixture was ground and mixed for 10 minutes using the vibrating mill of Example 2, and 4 tons of the mixture was placed in the mold of Example 1. After preforming with a press at 1.5 TON/cId, the mold temperature was applied. Raised to 340℃ under pressure o, 5TON/-5
The mixture was held for a minute, cooled to 200° C., the applied pressure and mold outer frame were released, and the mixture was cooled to room temperature. The resulting green body 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) The manufacturing process is simplified compared to the grinding and mixing method of menphase pitch.

Furthermore, compared to conventional techniques, it is a simple process that omits complicated steps after heat treatment.

(2) Since it uses mesophase-containing pitch that contains quinoline-soluble content, it has excellent caking properties and heat-meltability, so a wide range of molding conditions can be used, from room temperature molding to heat molding, and the properties of the molded product can also be improved. It can vary widely.

(3) Carbon composite molded bodies of inorganic compounds can be made.

(4) 0(5) that allows for easy compounding of metal components
Bulky - It is possible to create new molded objects that bring out the functionality of the material.

Patent applicant Mitsubishi Yuka Co., Ltd. agent Hidere Furukawa Patent attorney Masahisa Hase Procedural amendment (voluntary) May 1985 98 1. Indication of case Patent application No. 255270 of 1982 Title of the invention: Method for producing carbon-based composite molded articles 3, Relationship with the case of the person making the amendment Patent applicant address: 2-5-2 Marunouchi, Chiyoda-ku, Tokyo Name (
605) Mitsubishi Yuka Co., Ltd. 4, agent voluntarily 6, subject of amendment 7, amend the statement of contents of the amendment as indicated.

(1) Page 19, line 14 "5~b ℃/hour”.

that's all

Claims (1)

[Claims] 1. Carbon made of one or more materials selected from graphitic carbon, carbonaceous carbon, inorganic compounds, metals, and metal compounds, and carbonaceous or graphite derived from 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 are added to a tar distillate containing a mesophase pitch precursor. (2) heating the suspension system and distilling off the light fraction contained in the tar fraction by blowing inert gas or vacuum suction to remove the mesophase pitch precursor; a step of heat-treating at 350 to 500°C to produce a mesophase-containing pitch containing 5 to 90% quinoline soluble content on the surface of the material; (3) molding the carbonaceous precursor to form a mesophase pitch; (4) a step of subjecting the formed body to a carbonization or graphitization reaction in an inert atmosphere to contain carbon or graphite derived from the mesophase-containing pitch; 1. A method for producing a carbon-based composite molded body, characterized by using a process.