JPH06199577A - Production of carbon-carbon composite material - Google Patents

Abstract

PURPOSE:To produce a carbon-carbon composite material having a dense structure and excellent in mechanical characteristics by an easy method at a low cost. CONSTITUTION:Pitch fibers obtd. by spinning pitch as starting material or infusible fibers obtd. by making the pitch fibers infusible are mixed with inorg. powder or inorg. fibers, carbon powder having self-sinterability and an org. solvent to prepare a liq. mixture and this mixture is freed of the solvent, compacted, carbonized and graphitized. Pitch fibers obtd. by spinning pitch as starting material or infusible fibers obtd. by making the pitch fibers infusible are mixed with inorg. powder or inorg. fibers, carbon powder having self- sinterability, a material contg. a caking component and an org. solvent to prepare a liq. mixture and this mixture is freed of the solvent, compacted, carbonized and graphitized. The objective carbon-carbon composite material is produced.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a carbon-carbon composite material.

[0002]

2. Description of the Related Art Carbon-carbon composite materials (also referred to as C-C composites) are more conventional than conventional carbon materials.
Due to its high strength and excellent heat resistance, wear resistance, and oxidation resistance, it is a material for aircraft brakes, rocket nozzles and other aircraft and aerospace equipment; hot press die materials, high temperature bearings and other mechanical parts. Materials: Used or about to be used as biomaterials.

A conventional carbon-carbon cord composite material is obtained, for example, by impregnating a carbon fiber precursor with a pitch or a thermosetting resin under pressure, firing it, and repeating impregnation and firing a necessary number of times. Has been obtained. In this method, since the volatile component generated by the decomposition of the pitch or the thermosetting resin in the firing step forms bubbles, the complicated operation of impregnating the pitch portion or the thermosetting resin in the bubble portion and firing is repeated. There is a need. Despite the need for such complicated steps, the products obtained are porous and unsatisfactory in terms of density, and large products lack the uniformity.

Further, a method of decomposing a hydrocarbon gas in a high temperature furnace to deposit a decomposition product on the surface of carbon fiber (C
VD method) is also performed. However, this method requires uniform thermal decomposition for a long time under the condition that soot is not generated, and requires a high level technique for setting the conditions, so that it is difficult to be practically used.

[0005]

DISCLOSURE OF THE INVENTION As a result of earnest studies in view of the above-mentioned conventional state of the art, the present inventor has found that the pitch fibers before being infusibilized by spinning the raw material pitch are infusibilized. The infusible fiber obtained by shaping the liquid mixture containing at least the inorganic powder or the inorganic fiber and the organic solvent, or obtained by infusibilizing the pitch fiber before the infusibilization process in which the raw material pitch is spun or the pitch fiber It has been found that when the mixture containing at least the fused fiber and the inorganic powder or the inorganic fiber is molded under a specific temperature condition and then carbonized and graphitized, the problems of the prior art are greatly reduced.

That is, the present invention provides the following method for producing a carbon-carbon composite material: Pitch fiber obtained by spinning the raw material pitch or infusible fiber obtained by making it infusible, inorganic powder or inorganic fiber,
A method for producing a carbon-carbon composite material comprising mixing a carbon powder having self-sinterability and an organic solvent to prepare a liquid mixture, desolvating the liquid mixture, molding, and carbonizing / graphitizing ( Hereinafter referred to as the first invention of the present application). 2. Pitch fiber obtained by spinning the raw material pitch or infusible fiber obtained by making it infusible, inorganic powder or inorganic fiber and carbon powder having self-sintering property are mixed to prepare a mixture, which is used as a mold. The carbon-carbon is characterized in that it is subjected to molding by compressing the mixture at room temperature to 500 ° C. until the shrinkage ratio of the mixture reaches 10 to 70% of its maximum shrinkage ratio, and then carbonization / graphitization. A method for manufacturing a composite material (hereinafter referred to as the second invention of the present application). 3. Pitch fiber obtained by spinning the raw material pitch or infusible fiber obtained by making it infusible, carbon powder having self-sinterability and an organic solvent are mixed to prepare a liquid mixture, which is then desolvated A method for producing a carbon-carbon composite material, which comprises molding, carbonizing and graphitizing (hereinafter referred to as the third invention of the present application). 4. Pitch fiber obtained by spinning the raw material pitch or infusible fiber obtained by making it infusible, inorganic powder or a mixture of inorganic fiber and carbon powder having self-sinterability is put in a mold and the mixture shrinks. The rate is 10 to 70 of the maximum contraction rate
A method for producing a carbon-carbon composite material, which comprises performing compression at a temperature of room temperature to 500 ° C. until the content reaches 0.1%, and then carbonizing and graphitizing (hereinafter referred to as the fourth invention of the present application).

The first invention to the fourth invention of the present application will be described in detail below. In the following, when simply referred to as “the present invention”, the items common to the four inventions are shown.

(1). First Invention of the Present Application The raw material pitch used as the spinning material in the present invention may be derived from a raw material such as a coal-based or petroleum-based material. Also, the pitch itself may be either optically isotropic or optically anisotropic.

Spinning and infusibilization of the raw material pitch may be carried out according to a conventional method, and the conditions are not particularly limited. What is used as a fiber component in the present invention is usually pitch fiber obtained by feeding raw material pitch to a spinning machine and extruding from a nozzle under pressure with an inert gas in a state of being heated to about 300 to 400 ° C, or Pitch fibers are further infusible by being held in an oxidizing atmosphere at about 150 to 500 ° C. for about 0.5 to 5 hours before being subjected to the usual carbonization treatment (hereinafter referred to as such pitch fibers and Infusible fibers are collectively referred to as uncarbonized fibers). The uncarbonized fiber preferably has a fiber length of about 0.01 to 30 mm and a fiber diameter of about 5 to 25 μm.

Examples of the inorganic powder used in the present invention include alumina, silica, titanium boride, titanium oxide, titanium nitride and chromium nitride. The particle size of the powder is not particularly limited, but is usually 0.01 to 1000 μm.
It is about m, and more preferably about 0.1 to 1 μm. Alternatively, examples of the inorganic fiber include fibers such as alumina, titanium boride, titanium oxide, titanium nitride, and chromium nitride. The fiber diameter and fiber length of the inorganic fiber are not particularly limited, but are usually about 1 to 30 μm and 0.01 to 40 mm, respectively, and more preferably about 5 to 20 μm and 0.1 to 30 mm, respectively. is there.

The self-sintering carbon powder used in the present invention may be either petroleum-based or coal-based carbon powder, and specifically, mesocarbon microbeads, bulk mesophase crushed products, low temperature calcination. Examples include crushed coke and crushed raw coke. Among these, petroleum-based and coal-based mesocarbon microbeads are preferable from the viewpoint of particle size and composition uniformity, stability, and the like, and from the viewpoint of carbonization yield, coal-based mesocarbon microbeads are more preferable.
The self-sintering carbon powder preferably has a particle size of 30 μm or less and a β-resin amount of about 3 to 50%.

The mixing ratio of each component in the molding mixture in the first invention of the present application is such that 1 part of uncarbonized fiber is added to 100 parts of carbon powder having self-sinterability (parts by weight: the same hereinafter).
About 200 parts (more preferably about 5 to 100 parts), 1 to about 200 parts of inorganic powder or inorganic fibers (more preferably about 5 to 50 parts).

In the first invention of the present application, the carbon powder, the uncarbonized fiber and the inorganic powder or the inorganic fiber having the self-sinterability in the above proportions are added to an organic solvent such as acetone, toluene, ethanol or methanol and mixed to form a liquid state. After preparing the mixture, the solvent is removed, the mixture is molded, and carbonized and graphitized. By using this organic solvent, it is possible to uniformly disperse the uncarbonized fiber and the inorganic powder or the inorganic fiber. In addition, uncarbonized fiber having a large fiber length (for example, a fiber length of 10
The dispersion of (mm or more) is also good. Acetone and / or toluene are more preferable as the organic solvent. The mixing means is not particularly limited as long as the components are uniformly mixed in the organic solvent, and examples thereof include stirring by ultrasonic irradiation and mechanical stirring. In particular, stirring with ultrasonic irradiation improves the dispersibility of each component. The solid content concentration in the liquid mixture is not particularly limited as long as a uniform mixture can be formed, but is usually about 5 to 80% (representing weight%: the same below), and more preferably 20 to 50%. It is a degree.

In the first invention of the present application, a material containing a caking component such as tar, pitch, organic polymer (phenol resin, polyvinyl chloride, polyvinyl alcohol, etc.) may be used in combination. By using this binder-containing material together, uncarbonized fiber, inorganic powder or inorganic fiber,
The dispersibility in a liquid mixture such as carbon powder having self-sinterability is further improved. The compounding amount of the material containing the caking component is 1 with respect to 100 parts of the self-sintering carbon powder.
It is about 100 parts (more preferably about 5 to 50 parts).

The liquid mixture thus obtained is desolvated by a means such as filtration and then molded. The molding may be performed in the same manner as the known carbon powder having self-sinterability, and in this case, for example, 1 to 10 ton / cm ^2.
It may be formed into a predetermined size under a certain amount of pressure. Alternatively,
Molding may be performed by the CIP method or the like. Molding is 2
It can be performed at a temperature from room temperature of about 0 ° C. to about 500 ° C. (more preferably about 100 to 400 ° C.).
When molding in a heated state, to prevent oxidation,
It is preferably carried out in an inert atmosphere.

In the present invention, after the above liquid mixture is desolvated, it is housed in a mold and the shrinkage ratio of the mixture is maximum at a temperature from room temperature to about 500 ° C. (more preferably about 100 to 400 ° C.). It is more preferable to carry out molding by compressing at a pressure of 10 to 70% of the ratio. In particular, when molding is performed by such a method under heating, the caking component (β-resin) existing on the surface of the carbon powder having self-sintering property such as mesocarbon microbeads melts and flows. As compared with the case of molding at room temperature, a compact body having a dense structure can be obtained at a lower pressure. Further, the internal stress and strain generated inside the molded body due to the application of pressure are similarly relaxed.

Here, the maximum contraction rate is defined as follows. That is, when the raw material mixture after desolvation is housed in a bottomed cylinder and the cylinder is heated from room temperature to 500 ° C. while applying a load to the upper piston, the volume of the raw material mixture gradually increases due to melting of the caking component. The height of the raw material mixture in the cylinder is reduced. The reduction value (shrinkage amount) of this height divided by the initial height is called the shrinkage ratio, and the shrinkage ratio at the time when the shrinkage amount is maximum is the maximum shrinkage ratio. This shrinkage amount or maximum shrinkage amount varies depending on the composition of the raw material mixture, but the value can be easily obtained by an experiment.

The firing may be carried out under the same conditions as the known sintering of a carbon powder compact having self-sintering property, and is not particularly limited, but is usually 0.1 to 300 ° C. in a non-oxidizing atmosphere.
The temperature may be raised from room temperature to a temperature of about 1300 ° C. at a speed of about / hour and held for about 0.5 to 10 hours.

The obtained sintered body is then graphitized.
The conditions for graphitization are also not particularly limited, and the temperature at the time of sintering in a non-oxidizing atmosphere is raised to a temperature of about 1500 to 3000 ° C. at a rate of about 0.1 to 500 ° C./hour, and 0.5 ~
It should be held for about 10 hours.

(2). Second invention of the present application The raw material pitch used as the spinning material in the second invention of the present application is
This is the same as that used in the first invention of the present application, and the production of pitch fibers by the spinning and the infusibilization of the pitch fibers are performed in the same manner as in the first invention of the present application. The same inorganic powder, inorganic fiber, or self-sintering carbon powder as those used in the second invention of the present application are also used.

In the second invention of the present application, tar,
A material containing a binding component such as pitch or an organic polymer (phenol resin, polyvinyl chloride, polyvinyl alcohol, etc.) may be used in combination. By using this binder-containing material together, the dispersibility in a mixture of uncarbonized fiber, inorganic powder or inorganic fiber, carbon powder having self-sinterability, etc. is further improved.

The mixture in the second invention of the present application is about 1 to 200 parts (more preferably about 5 to 100 parts) of uncarbonized fiber with respect to 100 parts of carbon powder having self-sinterability (representing parts by weight; the same applies hereinafter). ), Inorganic powder or inorganic fibers 1 to
About 200 parts (more preferably about 1 to 50 parts) or, if necessary, a material containing a caking component 1 to 100
It is prepared by adding about 1 part (more preferably about 5 to 50 parts) and mixing.

In the molding according to the second invention of the present application, the mixture described above is housed in a mold, and the shrinkage ratio of the mixture is 10 to the maximum shrinkage ratio at a temperature from room temperature to about 500 ° C. (more preferably about 100 to 400 ° C.). It is performed by compressing at a pressure of ˜70%.

The molding may be fired in the same manner as in the first invention of the present application.

(3). Third Invention of the Present Application In the third invention of the present application, a mixture having the same composition as that of the first invention of the present application except that it does not contain inorganic powder or inorganic fibers is desolvated, and then housed in a mold to perform the same process as the first invention of the present application. And mold.

The molded body obtained by the above method in the third invention of the present application is carbonized and graphitized in the same manner as in the first invention of the present application or the second invention of the present application to obtain a desired carbon-carbon composite material. To be

(4). Fourth invention of the present application In the fourth invention of the present application, a mixture having the same composition as the second invention of the present application except that the inorganic powder or the inorganic fiber is not contained is housed in a mold and molded in the same manner as in the third invention of the present application. To do.

The molded body obtained by the above method in the fourth invention of the present application is carbonized / graphitized in the same manner as in the first to third inventions of the present application to obtain a desired carbon-
A carbon composite material is obtained.

[0029]

【The invention's effect】

(1) In the first invention of the present application and the third invention of the present application using an organic solvent, the wettability between the uncarbonized fiber and the self-sintering carbon powder and the organic solvent is good, and therefore mixing is easy.
As a result, even if an uncarbonized fiber having a large fiber length is used, a pill does not occur, and a liquid mixture in which the respective components are uniformly dispersed can be obtained. Furthermore, when mixing, it is possible to perform stirring by ultrasonic irradiation of an organic solvent,
Dispersion of the inorganic powder and / or the inorganic fiber is also facilitated. (2) When a binder-containing material such as tar is used in combination, the wettability of uncarbonized fiber, self-sintering carbon powder, etc. with an organic solvent is further improved, so more uniform mixing is possible. Becomes (3) As a result of the above (1) and (2), a high density carbon-carbon composite material having excellent mechanical properties such as strength can be obtained. (4) Further, when the mesocarbon microbeads are used as the self-sintering carbon powder, the caking component (β-resin) existing on the surface of the bead melts during molding, so that the fluidity as a molding material is high. A molded body having a high density and a dense structure can be obtained at a low pressure, and thus a carbon-carbon composite material excellent in various characteristics can be obtained. Further, the internal stress and strain generated during the pressure molding are relaxed by the flow of the caking component (β-resin). (5) Also in the second and fourth inventions of the present application, the uncarbonized fiber and the self-sintering carbon powder are melted by melting the caking component (β-resin) present on the surface of the self-sintering carbon powder during molding. Since it is well compatible with, a molded product having a dense structure can be obtained at a low pressure even when an organic solvent does not exist in the molding material, and thus a carbon-carbon composite material excellent in various characteristics can be obtained. .

[0030]

EXAMPLES Examples and comparative examples will be shown below to further clarify the features of the present invention.

Example 1 Infusible fibers (fiber diameter 15 μm, fiber length 0.5 mm) 230 obtained by a conventional method from coal-based optically isotropic pitch 230
Dispersion containing 530 parts of coal tar-based mesocarbon microbeads having a central particle size of 7 μm, uniformly mixed in 800 parts of acetone, and further containing 50 parts of alumina powder (particle size 0.5 μm) in 100 parts of acetone. Were mixed under ultrasonic irradiation to obtain a liquid mixture, which was then filtered.

The resulting mixture is molded at a molding pressure of 2 ton / cm ^2.
With a molding pressure of 50 mm in diameter and 10 mm in length, and heated to 1000 ° C. at a rate of 150 ° C./hour,
After holding at the same temperature for 1 hour for firing, it was heated to 2800 ° C. at a rate of 500 ° C./hour and kept at the same temperature for 20 minutes.

Thus, a carbon-carbon composite material having a density of 1.82 g / cm ³ and a bending strength of 900 kgf / cm ² was obtained.

Comparative Example 1 300 parts of carbonized fibers (fiber diameter 15 μm, fiber length 0.5 mm) obtained by a conventional method from coal-based optically isotropic pitch, and coal tar-based mesocarbon microbeads having a central particle diameter of 7 μm 700 parts was added and mixed by a dry method, and further 50 parts by alumina powder (particle size: 0.5 μm) was mixed by a dry method. Thereafter, a carbon-carbon type composite material was obtained in the same manner as in Example 1. The physical properties were uniform, but the density was 1.74 g / c.
m ³ and bending strength of 480 kgf / cm ² , which were inferior to the products of the present invention.

Example 2 300 infusible fibers (fiber diameter 15 μm, fiber length 0.5 mm) obtained from a coal-based optically isotropic pitch by a conventional method
700 parts of coal tar-based mesocarbon microbeads having a central particle size of 7 μm was added to the above parts and mixed by a dry method, and further 50 parts of alumina powder (particle diameter 0.5 μm) was mixed by a dry method.

The obtained mixed powder was heated to 450 ° C. at a heating rate of 8 ° C./min under reduced pressure (76 mmHg). When the temperature of this mixed powder reaches 300 ° C, 500 kg / c
A molding pressure of m ² was applied for 1 minute. Obtained diameter 50m
m × 10 mm length molded body 1 at a rate of 150 ° C./hour
The temperature was raised to 000 ° C., and the temperature was kept at the same temperature for 1 hour for firing. Then, the temperature was raised to 2800 ° C. at a rate of 500 ° C./hour, and the temperature was kept for 20 minutes.

Thus, a carbon-carbon composite material having a density of 1.83 g / cm ³ and a bending strength of 920 kgf / cm ² was obtained.

Example 3 300 infusible fibers (fiber diameter 15 μm, fiber length 0.5 mm) obtained by a conventional method from coal-based optically isotropic pitch
FIG. 1 shows the melting characteristics of a mixture obtained by adding 700 parts of coal tar-based mesocarbon microbeads having a central particle size of 7 μm to the above parts and mixing them in a dry manner during heating under pressure. Result is,
The mixture was filled in a cylinder having an inner diameter of 50 mm and a depth of 100 mm (initial packing density 0.979 g / cm ³ ), and the temperature was raised at a rate of 8 ° C./minute while pressurizing from above with a piston pressure of 150 kg / cm ² . In this case, the maximum drop value of the piston (that is, the maximum shrinkage ratio of the molded body) is set to 100, and the relative value is shown. Shrinkage rate of the molded product at 300 ℃ 5
It is clear that it was 6%.

The mixture obtained in the same manner as above was packed in the same cylinder as above (initial packing density 0.979).
g / cm ³ ) and the temperature was raised to 450 ° C. at a rate of 8 ° C./min. At that time, as shown in FIG. 2, the temperature of the mixture is 200 ° C., 250 ° C., 300 ° C., 310 ° C., 320 ° C., respectively.
When the temperature reached 350 ° C., 350 ° C. and 400 ° C., the pressure was increased to 500 kg / cm ² for 1 minute.

Each of the test pieces thus obtained was subjected to 45
After keeping at 0 ° C. for 1 hour, it was naturally cooled. Each of the obtained molded bodies having a diameter of 50 mm and a length of 10 mm was heated to 1000 ° C. at a rate of 150 ° C./hour, held at the same temperature for 1 hour and baked, and then heated to 2000 ° C. at a rate of 500 ° C./hour. It was heated and kept at the same temperature for 20 minutes. FIG. 3 shows the relationship between the temperature at the time of pressurization and the bending strength (upper curve) and density (lower curve) of the finally obtained sintered body.

Example 4 300 infusible fibers (fiber diameter 15 μm, fiber length 0.5 mm) obtained by a conventional method from coal-based optically isotropic pitch
700 parts of coal tar-based mesocarbon microbeads having a central particle size of 7 μm was added to the above parts, and mixed by a dry method.

The obtained mixed powder was heated to 450 ° C. at a heating rate of 8 ° C./min under reduced pressure (76 mmHg). When the temperature of this mixed powder reached 200 ° C, 150 kg / c
It is pressurized at a molding pressure of m ² until the temperature of the mixed powder reaches 250 ° C., then at a pressure of 300 kg / cm ² until the temperature of the mixed powder reaches 275 ° C., and further 500 kg / cm.
The pressure of ² was applied until the temperature of the mixed powder reached 300 ° C. 1 piece of the obtained molded body having a diameter of 50 mm and a length of 10 mm
After heating up to 1000 ° C. at a rate of 50 ° C./hour, holding at the same temperature for 1 hour and firing, 2 at a rate of 500 ° C./hour
It was heated to 000 ° C. and kept at the same temperature for 20 minutes.

Thus, a carbon-carbon composite material having a density of 1.82 g / cm ³ and a bending strength of 1030 kgf / cm ² was obtained.

Example 5 Infusible fibers (fiber diameter 15 μm, fiber length 0.5 mm) obtained by a conventional method from coal-based optically isotropic pitch and infusible fibers having different fiber diameters (fiber lengths 6 mm and 12 mm) )
And coal tar-based mesocarbon microbeads having a central particle size of 7 μm were mixed in acetone at the following weight ratio (solid content concentration 50%), and then filtered.

The obtained mixed powder was heated to 450 ° C. at a heating rate of 8 ° C./min under reduced pressure (76 mmHg). When the temperature of this mixed powder reached 200 ° C, 150 kg / c
It is pressurized at a molding pressure of m ² until the temperature of the mixed powder reaches 250 ° C., then at a pressure of 300 kg / cm ² until the temperature of the mixed powder reaches 275 ° C., and further 500 kg / cm.
The pressure of ² was applied until the temperature of the mixed powder reached 300 ° C. 1 piece of the obtained molded body having a diameter of 50 mm and a length of 10 mm
After heating up to 1000 ° C. at a rate of 50 ° C./hour, holding at the same temperature for 1 hour and firing, 2 at a rate of 500 ° C./hour
It was heated to 000 ° C. and kept at the same temperature for 20 minutes.

The density and bending strength of the thus obtained sintered body are also shown below.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] March 2, 1994

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] Brief description of the drawing

[Correction method] Added

[Correction content]

[Brief description of drawings]

FIG. 1 is a graph showing the relationship between the temperature during molding of a carbon-carbon composite material obtained by the method of the present invention and its shrinkage rate.

FIG. 2 shows a carbon-carbon composite material obtained by the method of the present invention.
It is a graph which shows the relationship between time and pressure when pressurizing at a pressure of 00 kg / cm ² .

FIG. 3 is a graph showing the relationship between the temperature of the carbon-carbon composite material obtained by the method of the present invention during pressurization and the bending strength and density of the sintered body.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Norio Murakami 4-1-2, Hirano-cho, Chuo-ku, Osaka, Osaka Gas Co., Ltd. (72) Inventor Hirohisa Miura, Toyota-cho, Toyota-shi

Claims (13)

[Claims] 1. A pitch fiber obtained by spinning a raw material pitch, or an infusible fiber obtained by infusibilizing the pitch fiber, an inorganic powder or an inorganic fiber, a carbon powder having self-sinterability, and an organic solvent are mixed to form a liquid. A method for producing a carbon-carbon composite material, which comprises preparing a mixture, desolvating the mixture, molding the mixture, and carbonizing / graphitizing the mixture. 2. A pitch fiber obtained by spinning a raw material pitch or an infusible fiber obtained by making it infusible, inorganic powder or a mixture of inorganic fiber and carbon powder having self-sintering property, This is put in a mold, and the mixture shrinks from room temperature to 50 until the shrinkage of the mixture reaches 10 to 70% of its maximum shrinkage.
A method for producing a carbon-carbon composite material, which comprises performing compression by compression at a temperature of 0 ° C. and then carbonizing and graphitizing. 3. A liquid mixture is prepared by mixing pitch fibers obtained by spinning raw material pitch or infusible fibers obtained by infusibilizing the pitch, self-sintering carbon powder and an organic solvent. The method for producing a carbon-carbon composite material, which comprises desolvating, then shaping, and carbonizing / graphitizing. 4. A mixture of pitch fibers obtained by spinning a raw material pitch or infusible fibers obtained by infusibilizing this and inorganic powder or a mixture of inorganic fibers is placed in a mold and the mixture is mixed. A method for producing a carbon-carbon composite material, which comprises performing compression by compressing at a temperature from room temperature to 500 ° C. until the shrinkage ratio becomes 10 to 70% of the maximum shrinkage ratio, and then carbonizing / graphitizing. 5. The method for producing a carbon-carbon composite material according to claim 1, wherein the liquid mixture further contains a caking component-containing material. 6. The method for producing a carbon-carbon composite material according to claim 2, wherein the mixture further contains a caking component-containing material. 7. The method for producing a carbon-carbon composite material according to claim 3, wherein the liquid mixture further contains a caking component-containing material. 8. The method for producing a carbon-carbon composite material according to claim 4, wherein the mixture further contains a caking component-containing material. 9. The mixture is placed in a mold and the shrinkage of the mixture is from room temperature to 50 until the shrinkage of the mixture reaches 10 to 70% of its maximum shrinkage.
The method for producing a carbon-carbon composite material according to any one of claims 1, 3, 5 and 7, wherein molding is performed by compression at a temperature of 0 ° C, and then carbonization and graphitization are performed. 10. The method for producing a carbon-carbon composite material according to claim 1, wherein the carbon powder having self-sinterability is mesocarbon microbeads. 11. The method for producing a carbon-carbon composite material according to claim 5, wherein the binder-containing material is tar, pitch or an organic polymer. 12. The heating temperature at the time of molding is 100 to 400 ° C.
The method for producing a carbon-carbon composite material according to claim 2, 4 or 9, which is within the range. 13. The method for producing a carbon-carbon composite material according to claim 1, wherein the organic solvent contains at least acetone and / or toluene.