JPS6059167B2 - Manufacturing method of carbon molded body - Google Patents

Description

[Detailed description of the invention] The present invention relates to a method for manufacturing a carbon molded body.

More specifically, it is a novel granular or powdered phenol that has good flow characteristics and reactivity, and exhibits excellent moldability and carbonization yield by itself or when mixed with various carbonized materials, fillers, etc.・Using formaldehyde resin,
The present invention relates to a method for producing a carbon molded body having excellent strength and high hardness. Conventionally, novolac resins and resol resins are known as representative phenol-formaldehyde resins. Novolac resins usually have a molar ratio of phenol to formaldehyde, e.g. 1:0.7 to 0.
．． It is produced by reacting phenol with formalin in the presence of an acid catalyst such as oxalic acid (usually 0.2 to 2%) under conditions in which there is an excess of phenol such that the amount of phenol is 9. The novolak resin obtained by such a method consists of 3- to
The pentamer is the main component, contains almost no free methylol groups, and therefore does not have self-crosslinking properties by itself and has thermoplasticity. The novolak resin is then reacted under heat with a cross-linking agent which is itself a formaldehyde generator and also an organic base (catalyst) generator, such as hexamethylenetetramine (hexamine), or with a solid acid catalyst such as paraformaldehyde, etc. A cured resin can be obtained by mixing with the resin and subjecting it to a heating reaction. Novolac resins are powdered and easy to handle, but when a molded product is heated and cured, the curing reaction proceeds from the surface of the molded product toward the inside, often resulting in a cured product whose interior is not sufficiently cured.

Therefore, when such a hardened product is subjected to carbonization firing, gas is generated inside the molded product, causing cracks and gas blisters in the molded product, and as the carbonization firing progresses, these cracks and gas blisters become more noticeable, resulting in unsatisfactory results. It is very difficult to produce quality carbon molded bodies. Furthermore, since resol resins are usually supplied as a solution, it is very difficult to remove the solvent and make a molded product by itself because the gelation reaction proceeds while foaming occurs during the removal of the solvent.

For this reason, it is common practice to use a filler substance to desolvent and mold the product, but when such a molded product is subjected to carbonization firing, gas blisters and cracks occur, similar to the case with the novolac resin described above. It is extremely difficult to produce carbon molded bodies of satisfactory quality in terms of strength or hardness. l
In addition, in relatively recent years, novolak resins have been heated at high temperatures to obtain products with a considerably high degree of condensation, and this has been purified to separate and remove low condensates, resulting in 7 to 1 methylene phenolic groups. A relatively high condensate bonded by groups is obtained, and this is heated and melt-spun to form a novolac resin fiber, which is immersed in a mixed aqueous solution of hydrochloric acid and formaldehyde, and heated gradually from room temperature for a long period of time. A method of producing cured novolac resin fibers by proceeding the curing reaction from the outside of the fibers was proposed (Japanese Patent Publication No. 11284/1984).

However, cutting or crushing the cured novolak fibers produced as described above is not only expensive, but also cannot be used as a molding material in the form of granules or powders with good flow characteristics.

A method for producing a carbon molded body from a molded body made of a composition of the above-mentioned cured novolac resin fibers and other carbonized materials has also been proposed very recently (Japanese Patent Laid-Open No. 77293/1983).
(see issue).

However, as mentioned above, cured novolac resin fibers are not granular or powdered resins with good flow characteristics, and are not reactive, so they always require other carbonized materials as binders. There are problems such as nozzle clogging during injection molding or difficulty in producing a molded article in which the fibers are uniformly dispersed. In addition, in recent years, hydrophilic polymer compounds have been added to the condensate obtained by reacting phenols and formaldehyde in the presence of at least a nitrogen-containing compound.
A method for producing granular or powdered resin through reaction has been published (Japanese Patent Publication No. 53-142077), but the non-gelled resin obtained by this method contains a large amount of free phenol, about 5 to 6%. (Examples 1 to 4), and the gelled product (Example 5) not only becomes an extremely hard non-reactive resin, but also the resin does not absorb the nitrogen-containing compound or hydrophilic polymer compound used as a catalyst. contains.

Therefore, it not only deteriorates the performance of the molded product obtained by using it as a filler, but also reduces the performance of the molded product. It has the drawback of causing cracks and gas blisters in the carbon molded body. Furthermore, a method is known in which a prepolymer obtained by reacting phenol and formaldehyde in a basic aqueous solution is mixed with a protective colloid and coagulated into inert solid beads under acidic conditions (Japanese Patent Publication No. 51-13491). issue),
This corresponds to a so-called cured resol resin, which has no reactivity and also contains salts, acids, and other protective colloids, which similarly reduces the performance of molded products obtained by using it as a filler. In addition to this, it also has the disadvantage of causing cracks and gas blisters in the carbon molded product obtained from the molded product.

As mentioned above, attempts have been made to use phenol-formaldehyde resin as a filler in molded products, but
When viewed as a filler for molded products, it is difficult to obtain phenol-formaldehyde resin in a shape or form suitable for use as a filler, and it is also undesirable for molded products, especially molded products for carbonization. It has the problem of containing substances that have an impact. The inventors
Previously, we have provided a new phenol-formaldehyde resin in granular or powder form and a method for producing it, which do not have the above-mentioned drawbacks.

Therefore, an object of the present invention is to provide a method for producing a carbon molded body using a new granular or powdered resin as a carbonized material. Another object of the present invention is to provide a method for producing a carbon molded body having excellent strength and high hardness using a granular or powdery resin having good flow characteristics as a carbonized material. It's about doing.

Still another object of the present invention is to produce a carbon molded body with a high carbonization yield from a precursor molded body (a molded body for carbonization) using the granular or powdered resin as a carbonization material. The goal is to provide a way to do so.

Still another object of the present invention is to use a granular or powdered resin that is reactive with itself or with other resins as a carbonization material, so that cracks and gas blisters are reduced, and the interior and exterior are bonded. It is an object of the present invention to provide a method for producing a precursor molded body with almost no unevenness in quality, and thus producing a carbon molded body having no cracks or gas blisters and having a homogeneous inside and outside.

Still another object of the present invention is to provide a method for producing a sponge-like carbon molded body having excellent strength and high hardness.

Still another object of the present invention is to provide a method for producing a carbon molded body having excellent strength, high hardness, and an extremely large specific surface area.

Still another object of the present invention is to provide a method for producing a carbon molded body having excellent strength and high hardness and exhibiting conductivity ranging from a conductor to a semiconductor.

Still another object of the present invention is to provide a method for producing a carbon molded article that has excellent strength and high hardness, and also exhibits excellent heat resistance, wear resistance, sliding properties, and chemical resistance. be.

Further objects and advantages of the present invention will become apparent from the following description.

Such objects and advantages of the present invention are, according to the present invention, (
4) Contains spherical primary particles and secondary aggregates with a particle size of 0.1 to 150 microns, and (B) has an absorption intensity of 1600 cTn-1 in the range of Dl6OOl99O to 1015 cm-1 in the infrared absorption spectrum by KBr tablet method. The highest absorption intensity is D99O″1015)890c
When the absorption intensity of m-1 is D89O, a thermoformable resin composition containing at least a granular or powdered phenol-formaldehyde resin, or a heat-formable resin composition of the granular or powdered phenol-formaldehyde resin, This is achieved by a method for producing a carbon molded body, which is characterized in that a precursor molded body is thermoformed from a moldable material alone, and then the precursor molded body is carbonized and fired.

The granular or powdered phenol-formaldehyde resin used in the present invention is composed of phenol or phenol containing at least (4)% by weight of phenol, especially at least 7% by weight, such as o-cresol, m-cresol, p-cresol, etc. -Cresol, bis-phenol A, sO-
, m- or p-C2-C4 alkylphenol, p-phenylphenol, xylenol, resorcinol, etc., and a mixture of one or more of the known phenol radicals such as formaldehyde and a condensate thereof.

The above-mentioned granular or powdered phenol formaldehyde resin used in the present invention is the above-mentioned (4) and (
It has the characteristics B). In the specification of (4) and (B) above, the specification that the particle size of the spherical primary particles and their secondary aggregates in (4) is 0.1 to 150 microns is determined by the measurement method described below. It is based on

The first characteristic of the above-mentioned granular or powdered phenol formaldehyde resin is that it is extremely difficult to crush a conventionally known cured product of novolak resin or cured product of resol resin, but it can be Completely different from the known pulverized cured novolac resin fibers, these are spherical primary particles and secondary aggregates thereof, as specified in (4) above, with a particle size of 0.1 to 150 microns, preferably Contains 0.1 to 100 microns. The granular or powdered phenol-formaldehyde resin usually has at least 30%, preferably at least 50%, spherical primary particles and secondary particles with a particle size of 0.1 to 150 microns, more preferably 0.1 to 100 microns. Consists of secondary aggregates. This indication of 30% or 50% means 30% of the total number of particles (including secondary aggregates) in one field of view of an optical microscope with a magnification of 100 to 100@, as defined in the particle size measurement method described below. % or 50%
That is what it means. Particularly preferred is one in which 70 to substantially 100% of the granular or powdered phenol-formaldehyde resin consists of spherical primary particles and secondary aggregates having a particle size of 0.1 to 150 microns. Particularly preferred are at least 30 particles (as the average value of 5 fields) of the optical microscopic field according to the above definition.
%, especially at least 50% of which 70 to substantially 100%
is 0.1 to 100 microns, more preferably 0.1 to 5
It consists of spherical primary particles in the 0 micron range and their secondary aggregates.

As mentioned above, the above granular or powdered phenol formaldehyde resin is formed mainly of the above spherical primary particles and microparticles of secondary aggregates thereof, so it is extremely small and the whole is extremely small. At least 5% by weight, preferably 7% by weight, particularly preferably at least 8% by weight of the total, passes through a 100 sieve mesh.

This indication that the granular or powdered phenol-formaldehyde resin used in the present invention is passed through the sieve is indicated by the fact that the granular or powdered resin is lightly rubbed by hand or brushed. A force that does not forcibly destroy the particles (including secondary aggregates) is applied, such as lightly pushing or smoothing the particles on the sieve with a sieve, or tapping them with your hand. This does not exclude anything. Furthermore, as specified in (B) above, the granular or powdered phenol-formaldehyde resin used in the present invention has the following properties in the infrared absorption spectrum:
It has the following characteristics.

Further, preferred granular or powdered phenol/formaldehyde resins used in the present invention are D89O~
1015/Dl6CX) is 0.3 to 7. Especially from 0.4 to
5.0, and DB9O/Dl6l is 0.1 to 0.
．． 9s especially has a characteristic of 0.12 to 0.8.

In the infrared absorption spectrum, the Dl6OO peak shows absorption attributed to the benzene nucleus, and D98O~1015
It is already widely known regarding phenol-formaldehyde resins that the peak D89O shows an absorption attributed to the methylol group, and the peak D89O shows an absorption attributed to the isolated hydrogen atom of the benzene nucleus.

The granular or powdered phenol-3 formaldehyde resin used in the present invention is D99O''1015/Dl6OO:
The characteristic value of 0.2 to 9.0 means that the granular or powdered phenol formaldehyde resin used in the present invention contains at least a certain amount of methylol groups, and the methylol group content is This shows that it can change considerably.

Especially D99O~10,,=0.3~7.0, especially 0.4
5.0, the phenol-formaldehyde resin preferably used in the present invention contains an appropriate concentration of methylol groups and is more stable.

Furthermore, D89O/Dl. in the infrared absorption spectrum of the granular or powdered phenol formaldehyde resin used in the present invention. O=0.09-1. A more suitable resin is D89O/Dl6CO=0.1-0.9s, of which 0
．． The fact that the granular or powdered phenol-formaldehyde resin used in the present invention exhibits a characteristic of 12 to 0.8 is due to the fact that the reactive sites (ortho and para positions) of the phenol skeleton are significantly affected by methylene bonds or methylol groups. Indicates the fact that it is moderately blocked.

Cured products of conventionally known resol resins are generally D99O″
1015/DllO and/or D89O/Dl6OO are the lower limits of the above characteristic values of the phenol-formaldehyde resin used in the present invention? Also, the novolac resin cured with hexamine has a D89.

/D1&). The characteristic value of is generally lower than the lower limit of 0.09 of the phenol-formaldehyde resin used in the present invention. According to elemental analysis, the granular or powdered phenol-formaldehyde resin used in the present invention is found to consist essentially of carbon, hydrogen, and oxygen, and to have the following composition (total weight: 10%): .

The above granular or powdered phenol formaldehyde resin further has a free phenol content of 500 ppm or less as measured by liquid chromatography,
Preferred products have a free phenol content of less than 400 ppm, especially less than 300 ppm.

The granular or powdered resin obtained by the method disclosed in Japanese Patent Publication No. 53-42077 contains 0.3 to about 6% by weight.
In contrast, the granular or powdered phenol used in the present invention contains an extremely large amount of free phenol.
The free phenol content of formaldehyde resins is thus extremely low, making its handling extremely easy and safe. The granular or powdered phenol-formaldehyde resin used in the present invention may be in either a state in which the curing reaction has not progressed sufficiently or in which the curing reaction has progressed relatively, according to the manufacturing method described later. You can also do it.

As a result, the granular or powdered phenol-formaldehyde resin used in the present invention has thermal properties such as (a ) At least a portion of the material is fused to form a lump or a plate, and (b) it is not substantially melted or welded and takes the form of granules or powder. Granular or powdered phenol of (a) above●
When the formaldehyde resin is heated to reflux at 10 V in 500 ml of substantially anhydrous methanol, the following formula is obtained: WO is the weight (q) of the resin used, W1
is the weight (y) of the resin remaining after heating and refluxing, and S is the methanol solubility (wt%) of the resin.

Furthermore, the granular or powdered phenol-formaldehyde resin used in the present invention is manufactured by a manufacturing method that does not substantially contain nitrogen-containing basic compounds or hydrophilic polymer compounds in the reaction system, as is clear from the manufacturing method described below. Since it is manufactured, it usually does not substantially contain nitrogen-containing basic compounds or hydrophilic polymer compounds. Such nitrogen-containing basic compounds and hydrophilic polymer compounds often cause cracks and gas blisters in the carbon molded body during carbonization firing. The above granular or powdered phenol◆formaldehyde resin used in the present invention is (
b) The following composition, hydrochloric acid (HCl) concentration of 5 to 28% by weight, (preferably 1
0 to 25% by weight, especially 15 to 2% by weight), formaldehyde (HCHO) concentration is 3 to 25% by weight (preferably 5% by weight).
-2% by weight, especially 7-15% by weight), and the total concentration of hydrochloric acid and formaldehyde is 15-40% by weight (preferably 20-35% by weight, especially 25-32% by weight). In the formaldehyde bath, (b) the following formula, bath ratio = 1 of the above hydrochloric acid-formaldehyde bath
(c) bringing the phenol into contact with the hydrochloric acid-formaldehyde bath while maintaining the bath ratio expressed by weight of the phenol to be at least 8 or more (preferably 10 or more, especially 15 to 40);
and this contact is carried out so that the phenol forms a white cloud after contact with the bath (preferably a clear solution is formed before forming a white cloud), and then at least a pink granular or powdery solid is formed. It can be manufactured by performing a process such that it is formed.

Regarding the composition of the hydrochloric acid-formaldehyde bath in (1) above, in addition to the three conditions (a), (c), and (c) above, condition 2 is such that the composition is at least 2 or more, especially 2.5 or more, especially 3 or more. It is preferable to do so.

The upper limit of the molar ratio in the above condition 2 is not particularly limited, but is 20
Below, 15 or less is particularly suitable. The above molar ratio is especially 4
~15. Of these, 8 to 10 are preferred. The feature of the above production method is that a hydrochloric acid-formaldehyde aqueous bath having a fairly high concentration of hydrochloric acid (HCl) and containing an excess of formaldehyde relative to phenols is used, preferably at a bath ratio of 8 or more. The purpose is to contact the phenols at a large ratio of 10 or more. As mentioned above, such reaction conditions for phenol-formaldehyde are fundamentally different from the reaction conditions for producing conventionally known novolac resins and resol resins. At the stage before adding phenols to the hydrochloric acid-formaldehyde bath to generate cloudiness,
The bath is stirred so that the added phenols and the bath form a transparent solution as uniform as possible, and the period from the time when white turbidity is formed until the formation of a pale pink solid is as follows. It is preferable not to apply mechanical shearing force such as stirring to the bath (reaction liquid).

The phenol to be added may be the phenol itself, or may be a diluted phenol with formalin, hydrochloric acid sluice solution, water, or the like.

Further, the temperature of the hydrochloric acid monoformaldehyde bath when adding phenols (or a diluted solution thereof) is preferably 90°C or lower, particularly 70°C or lower.

When the temperature of the bath is higher than 40°C, especially higher than 50'C, the rate of reaction between phenols and formaldehyde becomes high. Preferably, it is added to the bath. Also in this case, since the reaction rate is high, it is preferred that the phenol, especially its dilute solution, be brought into contact with the bath in the form of a trickle or preferably fine droplets. The bath temperature is 40
℃ or higher, especially 50℃ or higher, when phenols or their diluted solutions are brought into contact with this bath, the higher the bath temperature, the faster the rate of reaction between phenols and formaldehyde. A white turbidity forms within a short time or instantaneously within several minutes, and a pink-colored granular or powdery solid is rapidly formed.

The temperature of the hydrochloric acid-formaldehyde bath is maintained at 40°C or less, preferably 5°C to 35°C, especially 100°C to 30°C, and phenols or the diluted solution thereof, preferably water, are added to this bath to prevent cloudiness. For granular or powdered solids that have undergone the desired reaction at a temperature of approximately 50°C or lower, preferably 45°C or lower, the hardening reaction has not progressed sufficiently, so they are generally heat-sealed at 100°C as described below. It shows heat fusion properties in the test.

On the other hand, the temperature of the hydrochloric acid-formaldehyde bath is maintained at 40° C. or lower, preferably 15° C. to 35° C., and substantially the entire amount of the phenol to be added or the diluted solution thereof is added to the bath under stirring to obtain a transparent solution. Forming a solution, then producing a white turbidity under non-stirring conditions, and then producing a light pink granular or powdery solid with or without increasing the temperature;
This solid is heated at a temperature above 50-°C, preferably at 70°C.
When the desired reaction is completed by heating to a temperature of 0 to 95°C, the curing reaction progresses more, so the heat fusion properties at 100'C are reduced or substantially eliminated, or even at higher temperatures, e.g. indicates thermal adhesiveness at 200°C or similar.
Even at such high temperatures, it has substantially no heat fusion properties.

The most suitable phenol to be used in the above method is phenol, but those containing at least 5% phenol, particularly at least 7% phenol, include o-cresol, m-cresol, p-cresol, and p-cresol. Cresol, bis-phenol A, . It may be a mixture with one or more of the known phenol derivatives such as O-, m- or P-C2-C4 alkylphenol, p-phenylphenol, xylenol, resorcinol.

The granular or powdery phenol-formaldehyde resin solids produced in the bath as described above and in which the desired reaction has been completed are separated from the hydrochloric acid-formaldehyde bath,
The desired product can be obtained by washing the product with water, preferably neutralizing the adhering hydrochloric acid with an alkaline aqueous solution, such as aqueous ammonia or methanolic aqueous ammonia, and then washing with water.

In this case, it is preferable to use aqueous ammonia for neutralization since the solid material obtained by maintaining the temperature at 50° C. or lower until the reaction is completed generally has a high solubility in methanol. The method of the present invention is carried out by first producing a precursor molded body by thermoforming from the above granular or powdered phenol formaldehyde resin alone or a resin composition containing at least the granular or powdered resin.

The above granular or powdered phenol used alone
The formaldehyde resin or the resin composition described above must naturally be thermoformable.

The above granular or powdered phenol used alone
As a formaldehyde resin, therefore, the above-mentioned phenol-formaldehyde resin (a) is one that is at least partially fused when held at a temperature of 100°C for 5 minutes according to the thermal fusion measurement method. A mixture with the above-mentioned phenol-formaldehyde resin (b) which does not substantially melt or fuse according to the same thermal fusion measurement method as the phenol-formaldehyde resin (a) is preferably used. In the latter case (mixture), (b
The phenol-formaldehyde resin of (a) acts as a filler and the phenol-formaldehyde resin of (a) acts as a binder in the precursor molding. In the case of the above resin composition containing a granular or powdered phenol-formaldehyde resin, the phenol-formaldehyde resin must have the property that at least a part of it fuses according to the thermal fusion measurement method. (a)
Or it does not need to be a mixture of (a) and (b).

That is, as long as the resin composition contains, in addition to the granular or powdered phenol-formaldehyde resin, a binder that enables thermoforming due to its presence, the granular or powdered phenol-formaldehyde resin has a fusible property. It does not have to be thing (a). In other words, the granular or powdered phenol-formaldehyde resin may be fusible (a) but not meltable or fusible (b) if there is another resin that can act as a binder. It is also used in the same way. As is clear from the foregoing, what is important in the present invention is that the granular or powdered phenol formaldehyde resin is used as a component of the precursor molded body, and that the resin is used in the precursor molded body. It is a filler, but not a binder.

Whether it is fusible (a) or not (b) must be considered when manufacturing the precursor molded body, but either (a) or (b) granular or powdered phenol/formaldehyde resin can be used. Regardless of the use, carbonization and firing will still yield a carbon molded body with excellent strength and hardness. In the method of the present invention, the precursor molded body is composed of a granular or powdered phenol-formaldehyde resin alone, and the granular or powdered resin has fusibility (a) and (b) it does not have fusibility. In the case of a mixture with the above-mentioned fusion bonding property, (a) accounts for at least 10% by weight of the total weight, more preferably 2% by weight, especially 3% by weight.

In the method of the present invention, the resin composition containing at least granular or powdered phenol formaldehyde resin is
In addition to the granular or powdered phenol-formaldehyde resin, other carbonized materials may be contained.
The carbonized material may be a curable resin (first carbonized material). Thermosetting resin is preferred as the first carbonized material. For example, resol resin, novolak resin,
Epoxy resin, furan resin, melamine resin, carbon resin, etc. are preferably used. These carbonized materials can act as binders, so when using such carbonized materials, the granular or powdered phenol/formaldehyde resin used together must have fusibility (a)
(b) may be present or absent. Regardless of the granular or powdered phenol-formaldehyde resin, these resins are the product of cloudy microparticles, which are the initial reaction product of phenols, which react with formaldehyde and grow, so the carbon content is low. is high and extremely stable at room temperature, and since it itself contains a considerable amount of methylol groups, it exhibits reactivity when heated, providing a precursor that is integrated with the first carbonized material. In addition, the granular or powdered phenol-formaldehyde resin used in the present invention is very fine and has a large surface area as described above, so it is easy to uniformly disperse with the first carbonized material. Therefore, even if it is used in a relatively small amount, by carbonization firing, a carbon molded body with a high carbonization yield, excellent airtightness, and no gas blisters can be obtained.
The fact that the granular or powdered phenol-formaldehyde resin used in the method of the present invention is excellent as a carbonization material is that when the precursor molded body is carbonized and fired at a temperature of 1000°C, for example, when the precursor molded body is a cured resol resin body, The carbonization yield is 50 to 54% by weight, whereas the precursor molded body consists of the above granular or powdered phenol/formaldehyde resin alone, or 5 parts of resol resin (as solid content) and the above granular or powdered phenol. - It is clear that when the mixture is made of a mixture with 5 parts of formaldehyde resin, the carbonization yield is 60-7% by weight. It is also known that when the granular or powdered phenol-formaldehyde resin used in the present invention is carbonized and fired at the same temperature without using it as a precursor molded body, the carbonization yield is 54 to 5% by weight. Taking this into consideration, the granular or powdered phenol-formaldehyde resin used in the present invention is reactive on its own and with other resins, so it can give a carbon molded body from a precursor molded body with a high carbonization yield. I can believe it. When the first carbonized material is mixed with the granular or powdered phenol/formaldehyde resin, heated and molded, and carbonized and fired, the precursor molded body made only of the carbonized material is carbonized and fired. It can be said that it is possible to give a carbon molded body with a higher carbonization yield than when using this method. The carbonized material used in the resin composition can also be a second carbonized material.

Examples of the second carbonized material include coke, anthracite,
Caking bituminous coal, pitch, or a cured product of thermosetting resin is preferably used. This second carbonized material has relatively low reactivity with the granular or powdered formaldehyde resin compared to the first carbonized material, but is itself already carbonized to a considerable extent or is relatively less reactive than the first carbonized material. It can be said that this method can provide a high carbonization yield.

Coke, anthracite, and cured thermosetting resins can act as fillers, pitch as binders, and caking bituminous coal as fillers or binders in the precursor moldings. Moreover, the carbonized material used in the resin composition can also be a third carbonized material.

As the third carbonized material, firstly, carbohydrates, carbohydrate derivatives, or natural products containing carbohydrates as main components, such as carbohydrates such as cellulose (rayon), starch, and sugar;
Carbohydrate derivatives such as carboxymethyl cellulose, hydroxyethyl cellulose, acetyl cellulose, or carbohydrate-based natural products such as wood flour, linters, coconut husk, rice husk, and grain flour; secondly, thermoplastic resins such as polyamide and polyvinyl acetate; , vinyl chloride, vinylidene chloride or polyacrylonitrile resin,
Alternatively, heat-infusible resins other than cured products of curable resins, such as polyvinyl alcohol or polyvinyl formal, are preferably used. The third carbonized material generally has a low carbonization yield, and a carbon molded body obtained by carbonizing and firing a precursor molded body using the third carbonized material has voids and often an activated inner wall. Give a void to have. That is, the carbon molded body is obtained as a porous body. According to the method of the present invention, even when a carbon molded body is obtained as such a porous body, it is possible to produce a carbon molded body that generally has high strength and high hardness. In the method of the present invention, the resin composition containing at least a granular or powdered phenol-formaldehyde resin may further contain an inorganic filler independently of the carbon molded article.

Unlike the above carbonized materials, the inorganic filler remains in the carbon molded body as it is or after being reduced without being carbonized even when the precursor molded body is carbonized and fired.

Therefore, such inorganic fillers, by remaining in the carbon molded body obtained, impart properties such as heat resistance and semiconductivity to the carbon molded body, or positively improve certain properties of the carbon molded body. It is used to improve the situation. For example, silica, alumina, silica/alumina, calcium carbonate,
Mention may be made of calcium silicates or precious metals such as gold, silver, palladium, platinum, etc. Porous carbon molded bodies containing noble metals can be used as catalysts for reactions in which such noble metals are used as catalysts. In the method of the present invention, granular or powdered phenol●
The above-mentioned resin composition containing at least formaldehyde resin comprises (1) granular or powdered phenol-formaldehyde resin and (11) curable resin (first carbonized material) and/or (Iiii) the above-mentioned second or 3 carbonized materials or inorganic fillers.

In the method of the present invention, when the precursor molded body is made of the resin composition, the granular or powdery phenol
The formaldehyde resin occupies at least 1 weight % of the total composition, and the granular or powdered phenol described above, the thermoformable formaldehyde resin (resin (a) described above) and/or the second carbonized Preferably, the ingredients alone or in total amount to at least 2% by volume of the total composition.

More preferably, the granular or powdered phenol-formaldehyde resin accounts for at least 2 weight percent of the total composition and the thermoformable granular or powdered phenol-formaldehyde resin and/or the second carbonized material Alone or in combined amounts, they represent at least 30% by weight of the total composition.

In particular, the granular or powdered phenol-formaldehyde resin accounts for 3% by weight of the total composition, and the thermoformable granular or powdered phenol-formaldehyde resin and/or the second carbonized material are used alone or in combination. It is particularly preferred that the amount accounts for at least 4% by weight of the total composition. In the method of the present invention, as described above, a precursor molded body is first produced by thermoforming from a granular or powdered phenol-formaldehyde resin alone or a resin composition containing at least a granular or powdered phenol-formaldehyde resin.

The resin composition can be produced by mixing the various constituent components as described above, for example, using a mixer, kneader, roller, etc., by a method known per se.

In order to mold the precursor molded body by thermoforming, in the case of granular or powdered phenol/formaldehyde resin alone, the temperature is at least at least the temperature at which the component (a) to be fused is melted (for example, about 50 to about 200°C). In the case of the above-mentioned resin composition, the resin composition may be processed by a method known per se, such as injection molding, press molding, or molding, at a temperature at least higher than the temperature at which the binder component therein melts (for example, about 100 to about 150'C). What is necessary is just to heat and pressurize it into a desired shape by molding etc.

All of these thermoforming methods involve external heating, but according to the present invention, a granular or powdered phenol-formaldehyde resin that is reactive with itself or with other resins and has very small particles and a large surface area is used. Therefore, not only when granular or powdered phenol/formaldehyde is used alone, but also when a resin composition is used, it is mutually uniformly dispersed with other resins and reacts uniformly with heating, so that it can be obtained. The precursor molded body is hardened substantially uniformly to the inside, and no decomposed gases that would cause cracks or gas blisters in the carbon molded body are generated during carbonization firing.

In contrast, in the case of precursor molded bodies manufactured using only resol resin, the degree of curing differs between the surface area where heat is applied by external heating and the interior area where heat is difficult to transmit, so in many cases the surface area is completely cured. This results in a molded product that is cured but has an uncured interior, which is not desirable for use as a carbon molded product. That is, when a precursor molded body whose inside is uncured is carbonized and fired, decomposition gas is generated from the inside, resulting in a carbon molded body having cracks and gas blisters. The method of the present invention is then carried out by carbonizing and firing the precursor molded body.

The carbonization calcination is preferably carried out at a temperature of about 450'C or higher, more preferably between about 500'C and about 2500C.

Carbonization firing is performed under a non-oxidizing atmosphere, usually an atmosphere that does not substantially contain molecular oxygen, such as nitrogen, helium,
The test is carried out in an atmosphere containing at least one selected from hydrogen and carbon monoxide as the main atmospheric gas. An appropriate temperature increase rate when performing carbonization firing differs depending on the thickness or airtightness of the precursor molded body.

In general, the thicker and more airtight the precursor molding, the
It is desirable to raise the temperature slowly. The heating rate is from about 10'C/hour to about 2000C/hour. The temperature and atmosphere of carbonization firing have a large influence on the properties of the obtained carbon molded body.

For example, when carrying out carbonization firing at a temperature of about 700°C to about 1000°C in an atmosphere of water vapor, carbon dioxide, a mixture thereof, or a mixture of these and the above-mentioned non-oxidizing gas, the specific surface area is relatively small. A large carbon molded body is obtained.

Further, for example, the conditions in which carbonization firing is carried out at about 5000C to about 800C are suitable for producing a carbon molded body with conductivity in the semiconductor range, and at about 800C to about 200C.
The conditions when carried out at 0° C. are suitable for producing a highly conductive carbon molded body suitable for heat exchanger vibes, electrodes, and the like.

According to the method of the present invention, as can be understood from the above description, a carbon molded body with high strength and hardness can be obtained as a high-density or low-density (porous body), or a carbon molded body with a large surface area can be obtained. Whether it is obtained as a solid or a small object, whether it is obtained as a substance exhibiting the conductivity of a semiconductor or a substance exhibiting the conductivity of a conductor, etc., depends on the type or amount ratio of the constituent components constituting the precursor molded body. Of course, this can be changed to a certain extent depending on the molding conditions of the precursor compact (for example, it is desirable to heat-form under high pressure to obtain a high-density carbon compact) or the carbonization firing conditions, such as atmosphere, temperature, etc. can.

The carbon molded article obtained by the method of the present invention consists essentially of amorphous carbon.

This means that the diffraction angle (2θ) is 23 to 24 in the X-line diffraction diagram.
This was confirmed by the presence of a broad peak near the temperature. It is also produced by carbonizing and firing at a relatively low temperature according to the method of the present invention using a granular or powdered phenol-formaldehyde resin, especially one that does not melt or fuse (b), and another resin that serves as a binder. The carbon molded body may develop a granular or powder-like interface by electrolytically etching the carbon molded body using the carbon molded body as an anode. The carbon molded article obtained by the method of the present invention has excellent strength and hardness, and also has excellent heat resistance and
Shows wear resistance, sliding properties, or chemical resistance.

Therefore, the carbon molded body obtained by the method of the present invention can be used, for example, in sliding materials such as bearings, gears, bearings, aircraft brakes, and motor brushes; and in corrosion-resistant materials such as heat exchangers, Raschig rings, bubbler catalyst carriers, etc. Heaters such as heaters for electronic equipment and solar house heaters; Insulating materials such as insulation boards for vacuum furnaces and protection tubes for high temperature furnaces; Electrodes for hydric soda, fuel cells, and scouring; Semiconductors, radio wave reflection Electricity such as umbrellas;
It can be suitably used for electronic parts, etc.

In addition, it has excellent strength, hardness, and wear resistance, so it can be used as typesetting or abrasive grains; it has excellent chemical resistance, so it can be used, for example, as biological aggregate, analytical equipment, or ceramic/glass processing. It can also be used as a tool. In addition, filters with a large specific surface area or containing catalytic metals or added through post-processing include filters such as air filters, ozone filters, water filters, and oil filters; adsorbents in car Canistani solvent recovery equipment; It can be suitably used as a catalyst for various reactions.

The present invention will be described in more detail below with reference to Examples.

10. Method for measuring 1-150μ particles: Sample approximately 0.1f1 from one sample.

Such sampling is carried out five times from different locations for one sample. One part of each approximately 0.1y sampled sample was placed on a slide glass for microscope observation.

To facilitate observation of the sample placed on a glass slide, the particles should be kept as similar as possible. Expand your aspirations so that they do not overlap. Microscopic observation is performed at locations where about 10 to 50 granular or powdery substances and/or secondary aggregates thereof are present in the field of view under an optical microscope.

It is usually desirable to observe at a magnification of 1σ to 103 times. stomach. The sizes of all particles present in the field of view under the light microscope are read and recorded using a tape measure in the field of view under the light microscope. 0.
The content (%) of particles with a size of 1 to 150 μ is determined by the following formula.

Content rate (%) of 0.1 to 150μ particles - ＼Kari 001 NO
NO: Total number of particles whose size was read under a microscope N1: Number of particles with a size of 0.1 to 150 μ out of NO. 0.1 to 150 μ as the average value of the results of 5 samples for one sample represents the content of particles.

Amount passed through a 2100 Tyler mesh sieve: After thoroughly kneading the dried sample by hand if necessary, approximately 10 f of it was accurately weighed, and a 100 Tyler mesh sieve was shaken in small portions over 5 minutes (sieve dimensions; 200mφ,
Shaking conditions: 200 RPM), and after adding the sample, shake for one more time.

The amount of passage through the 100 tile mesh is calculated using the following formula.

100 Tyler mesh passing amount (weight %) σ.

; Input amount (f) ω1: 100 Amount remaining on the sieve without passing through the Tyler mesh sieve (y) 3 Measurement of infrared absorption spectrum and determination of absorption intensity (see Figure 1 of the attached drawings) Co., Ltd. Using an infrared spectrophotometer (Yo 22) manufactured by Hitachi, Ltd., an infrared absorption spectrum was measured for a measurement sample prepared by a conventional KBr tablet method.

The absorption intensity at a specific wavelength was determined as follows. In the measured infrared absorption spectrum diagram, draw a baseline at the peak whose absorption intensity is to be determined.If the transmittance at the apex of the peak is expressed as Tp, and the transmittance of the baseline at that wavelength is expressed as Tb, then the specific The absorption intensity D at the wavelength is given by the following formula. Therefore, for example, the absorption intensity of the 890c7x-1 peak and 6(1)x-1
The ratio of the peak absorption intensity to the peak absorption intensity is given by the ratio of the respective absorption intensities (D89O/DO6OO) calculated using the above equation.

Approximately 5y of a sample passed through a heat-sealable 100 tyler mesh at 100°C was placed on two 0.
2TS! Prepare a material inserted between t-thick stainless steel plates, and apply an initial pressure of 50°C for 5 minutes using a heat press machine (manufactured by Shinto Metal Industry Co., Ltd., single-action compression molding machine) that has been preheated to 100°C.
Blessed with k9.

After releasing the press, the heat-pressed sample was taken out from between the two stainless steel plates. If the sample taken out is clearly fixed to form a flat plate due to melting or fusion, it is determined that the sample has fusion properties, and if there is almost no difference between before and after heat pressing, the sample is judged to have adhesive properties. It was judged to be infusible. 5. Accurately weigh about 10q of methanol-soluble sample (the exact weighed weight is W).

) and heat treated under reflux in about 500 mt of substantially anhydrous methanol. Glass filter (N
O. 3), and the filter residue sample was further washed on the filter with about 100 mt of methanol, and then the filter residue sample was dried at a temperature of 40° C. for 5 hours (the exact weighed weight is W1). Methanol solubility (S1
%) was calculated. Methanol solubility (S1% by weight) = V×
Quantification of 6-free phenol content: Approximately 10 f of the sample passed through a 100-meter mesh was accurately weighed.
Heat treated under reflux for 30 minutes in 190y of substantially anhydrous methanol.

The p liquid filtered through a glass filter (No. 3) was subjected to high performance liquid chromatography (60
00A) - The phenol content in the Kakeki liquid was quantified, and the free phenol content in the sample was determined from a separately prepared calibration curve. The operating conditions for high performance liquid chromatography are as follows.

The phenol content in the citrus liquid was determined from a previously prepared calibration curve (relationship between phenol content and peak height based on phenol).

Measurement is performed according to the 70H base value hydroxyl value measurement method (Cosmetic Raw Materials Standard Commentary, 1st edition, Yakuji Nipposha Showa 5Cfr., General Test Method 377).

100 which is cut off at the bulk density 100m1 index
Into the m1 graduated cylinder, place 2 above the edge of the graduated cylinder.
From C771, pour in the sample that has passed through the 100 tiler mesh.

The bulk density is determined by the following formula. Hardness of 0 carbon molded body It was measured using a Vickers microhardness tester under a load of 500k9.

The bending strength of a carbon molded body was measured according to JIS-K-6911.

Gas permeability of the 2-carbon molded body was measured by a volume change method using helium gas with an apparatus according to ASTM D-1434.

:3 Heat resistance of carbon molded bodyT. G. The weight loss starting temperature was measured using apparatus A.

14 The X-ray diffraction pattern sample of the carbon compact was crushed using a tungsten carbide Dix-type crusher,
It was measured with a diffractometer using a CuKa line using a nickel filter.

15 Electrical specific resistance of carbon molded body It was measured by the voltage drop method according to JIS-R-7202.

Reference Example 1: 1) In a 2e separable flask, 2 containing various compositions of hydrochloric acid and formaldehyde (listed in Table 1) was added.
Pour 1,500 g of each mixed aqueous solution at 5°C, and add 8% phenol and 5% phenol prepared using 3% formalin and water. A mixed aqueous solution containing formaldehyde (
25° C.) were added at 62.5 f each.

After adding and stirring for 4 seconds, the mixture was left to stand for 6 minutes. 6. While the mixture was standing still, some of the contents in each separable flask remained transparent (Rur in Table 1).
lNO. 1 and 20), some changed from transparent to cloudy (Run No. 3, 9 and 13 in Table 1), and some changed from transparent to cloudy and then changed to a pale pink color (Run No. 3, 9 and 13 in Table 1). Run NO.2, 4-8, 10-17
and 19).

When observed under a microscope, the material that had changed color to a pinkish color already contained lump-like substances, aggregates of spherical substances, and a small amount of powdery substances. Next, while occasionally stirring the contents of each separable flask, the temperature was further increased to 80°C by 6 minutes, and then the temperature was increased to 80°C.
A reaction product was obtained by holding one powder at a temperature of ~87C.
The reaction product thus obtained was washed with hot water at 40 to 45°C, treated with 3 powders at a temperature of 60°C in a mixed aqueous solution consisting of 0.5% by weight of ammonia and 5% by weight of methanol, and then pulverized again at 40°C. Washed with warm water at ~45°C and dried at 80'C for 2 hours. Table 2 shows the properties of the reaction products obtained from the mixed aqueous solutions of hydrochloric acid and formaldehyde of various compositions thus obtained. (2) On the other hand, the following experiment was conducted for comparison.

1e separable flask, distilled phenol 28
Add 2y, 3% formalin 369y, and 2% ammonia water 150f, and heat from room temperature to 7% while stirring.
The temperature was raised to 0°C in 6 batches, and further stirred and heated at a temperature of 70 to 77C for 9 batches.

Next, the mixture was allowed to cool, and dehydration was carried out by azeotropic distillation under a reduced pressure of 40 TsnHg while adding 300 f of methanol little by little. 700 Y of methanol was added as a solvent to take out a yellow-brown transparent resol resin solution. When a portion of the thus obtained resol resin was desolvated under reduced pressure, it foamed violently and turned into a gel. This gelled product was further heated at 160°C under nitrogen gas.
The 6 powders were thermally cured at a temperature of A small amount of powder that passed through a 100-meter mesh sieve was obtained. In this case, the thermosetting resol resin is extremely hard;
Even if various types of crushers, ball mills, or vibrating mills for fluorescent X-rays were used, it was extremely difficult to obtain a powder of 100 mesh size. ! The thermosetting resol resin powder thus obtained was treated with a mixed aqueous solution consisting of 0.5% by weight ammonia and 5% by weight methanol under the same conditions as described above, washed with warm water, and then dried. The properties of the samples thus obtained are shown in Table 2 under Run No. It was written and written as 2l. Next, add phenol 390y1 to the separable flask 1e.
370 g of 3% formalin, 1.5 y of oxalic acid, and 390 y of water were added, and the temperature was raised to 90°C with 6 powders while stirring, and the 6 powders were stirred and heated at a temperature of 90 to 9 (range). .

Next, add 1.0y of 35% by weight hydrochloric acid and further add 90-92%
The mixture was stirred and heated at a temperature of 6°C. Next, add 500 ml of water
Add y, cool, remove water with a siphon, and add 30w0n
Heated under reduced pressure of Hg at a temperature of 10 CfC for 3 hours.
The temperature was further increased, and the mixture was heated under reduced pressure at a temperature of 180° C. for 3 hours.
The obtained novolak resin was obtained as a tan solid upon cooling. This product had a softening temperature of 78 to 80°C and a free phenol content of 0.7% by weight as determined by liquid chromatography. The above novolak resin was pulverized, mixed with 15% by weight of hexamethylenetetramine, and the mixture was heat cured at a temperature of 16 (in the range) in nitrogen gas, and then ground in a ball mill to 10 % by weight.
I let it pass through the sieve of 0 Tyler Metshiyu.

The powder thus obtained was prepared under the same conditions as described above.
It was treated with a mixed aqueous solution consisting of 5% by weight ammonia and 5% by weight methanol, washed with warm water, and then dried. The properties of the sample thus obtained were determined by RurlNO. 2nd as 22
It is listed in the table. Furthermore, the above novolac resin was made with a pore size of 0.2
Using a spinneret with 5Tn, φ and 120 holes, 136~
Melt spinning was carried out at a temperature of 138°C.

The obtained spun yarn with an average fineness of 2.1 denier was treated with hydrochloric acid at a concentration of 1
．． The powder was immersed at a temperature of 20 to 21°C for 6 minutes in a mixed aqueous solution consisting of 1% by weight and 1% by formaldehyde concentration, and then
The temperature was raised to 7°C over a period of 5 hours, and the temperature was maintained at 97°C for 1 hour. The thus obtained cured novolak fibers were washed with warm water under the same conditions as described above, treated with a mixed aqueous solution consisting of 0.5% by weight ammonia and 5% by weight methanol, washed with warm water, and then dried. This material was ground in a ball mill. Rur] NO. 23 in Table 2.

1) Table 1 shows the total concentrations of hydrochloric acid, formaldehyde and acid salts and formaldehyde used, and the molar ratio of formaldehyde to phenol.

In addition, Table 2 shows the results of microscopic observation of the obtained samples.
The content of particles of 50 μ, 1 to 100 μ, and further 1 to 150 μ, the amount passed through the sieve (100 mesh bath) when the obtained sample is passed through a 100-meter mesh sieve, and the infrared absorption spectroscopy of the obtained sample. 990-101
The absorption wavelength intensity ratio (IR intensity ratio) of 5crf1-1 and 890CTn-1 to 1600c'1 is shown.

RurlNO. in Table 1. In experiments 1, 2, 3, 6, 17, and 20, many sticky resins and hard large lumps or plate-like substances were formed at the bottom of the separable flask.

Also, Run NO. In experiments 1, 2 and 20, only less than 49f of solids were obtained from the 50y of phenol used. Run NO. l, 2, 3,
1 to 50 listed in Table 2 for 6, l7 and 20
μ, content of 1-100μ and 1-150μ particles (%
) and 100 mesh bath (wt%) values are for granules or powders relative to total solids, including sticky resin, lumps, and platelets.

However, in these experiments, 1 to 50μ, 1 to 1 of only granular or powdery solids produced
Content (%) of 00μ and 1-150μ particles and 1
The 00 mesh bath (weight %) was the value shown in Table 2. From the above experimental facts including the results listed in Table 2, RurlNO. l, 2, 3,
6, l7 and 20 are not recommended as manufacturing methods.

However, even with these manufacturing methods, the granules or powders produced have characteristics that are fully included in the granules or powders of the present invention. . Reference Example 2 In each of five 20' reaction vessels, 2% hydrochloric acid and 11
A mixed aqueous solution consisting of formaldehyde of 10.24 to 11.65 k9 by weight% was adjusted to the bath ratio shown in Table 3.
I put it in.

To each flask, at a temperature of 23°C, with stirring,
A mixed aqueous solution consisting of 3.7% by weight of phenol and 3.7% by weight of formaldehyde was mixed with 1.8k9, 1.5k9, and 0, respectively.
．． 9k9, 0.7k9, 0.4k9 and 0.25k9
added. The bath ratios in this case are 7.3, 8.5, and 13.
5, 17.0, 28.9 and 45.6. In either case, when stirring was continued after adding the phenol mixed aqueous solution, the mixture suddenly became cloudy in 40 to 1 seconds, and at the same time, stirring was stopped and the mixture was allowed to stand still. As the internal temperature gradually rose, the contents gradually changed to a pale pink color, and three times after the contents became cloudy, a slurry-like or resin-like substance was observed in each case. Then - the contents of each were heated to 75°C with stirring.
The temperature was raised over 2 hours, and then stirred and heated at a temperature of 75 to 76°C for three times. In this case, in the system with a bath ratio of 7.3, a large amount of cured resin material adhered to the stirring rod, making stirring very difficult. Moreover, in both cases, the contents changed to a pale pink color and further turned red when the temperature was increased. Next, the contents were washed with water, and then treated with 6 powders at a temperature of 50°C in a mixed aqueous solution of 0.1% by weight ammonia and 55% by weight methanol, and further washed with warm water at 80°C for 6 cycles. .

The resulting granules, powders, or lumps were lightly kneaded by hand and dried at a temperature of 100° C. for 2 hours. The moisture content after drying was 0.2% by weight or less in all cases. The contents are samples 31, 32, 33, 34, from the side with the lowest reaction bath ratio.
35 and 36. Table 3 shows the maximum temperature reached in the reaction system from the start of the reaction until 3 minutes after it became cloudy, the yield of the reaction product, the presence or absence of spherical primary particles as observed by microscopy, and the percentage of 100% of the reaction product. The content of the material passing through the Tyler mesh, the thermal fusibility of the reaction product at 100°C, the elemental analysis value of the reaction product, and the OH group value of the reaction product were shown.

In Table 3, Run NO. The 0H group value of No. 22 product varied widely and could not be measured.

In Table 3, the RLlIlNO3l experiment produced plates and lumps amounting to about 70% of the total solids formed at the bottom of the flask.

Granules or powders accounted for only about 30% of the total solids produced, but about 95% of them passed through a 100 mesh sieve. Note that Run NO. The reason why the presence or absence of spherical primary particles in 3L is small is because the proportion of granular or powdery substances in the solid matter is as small as about 30%.
Therefore, Run NO. Although the method of 3L is not recommended as a manufacturing method, the produced granules or powders are included in the granules or powders of the present invention. Run NO. 3l~
Almost all of the 36 granular or powdery substances are 1-
The particle size was 100μ. Reference Example 3 18% by weight was added to each of the 5 1e separable flasks.
1000 y of a mixed aqueous solution at 25°C containing 9% by weight of hydrochloric acid and 9% by weight of formaldehyde was added.

Room temperature was 15°C. While stirring each of these,
A diluted solution prepared by diluting 40 y of phenol with 5 q of water,
I put it into each at once. In both cases, stirring was stopped for 50 seconds after the diluent was added and the mixture stood still, but after 62 to 6 minutes after the diluent was added, it suddenly became cloudy and a milky white product was observed. gradually changed color to ping. The temperature of each liquid gradually rose from 25℃, and after adding the diluted liquid,
It reached a peak of 35-36'C in 6-17 minutes and dropped again. After adding the diluent, 0. Chichima (Run-ka.41)
, 1 hour (Runyo.42), 2 hours (RLlrlNO
．． 43), 6 hours (Run NO. 44), 24 hours (R
urlNO. 45), after being left at room temperature for n hours (Run No. 46), the contents were washed with water, treated in 1% by weight ammonia water at a temperature of 15 to 17°C for 6 hours, washed with water, dehydrated, and heated to 40°C. Dry at temperature for 6 hours. In Table 4,
Passage rate of the obtained dry sample through a 100-meter mesh sieve,
1. R intensity ratio, methanol dissolution amount, and free phenol content are shown.

In addition, Run NO. 4l~Run NO. All 46 samples were fused at a temperature of 60° C. in the thermal fusion bonding test. In FIG. 1 of the accompanying drawings, Run NO. The infrared absorption spectra of 44 samples are shown. Figure 1 shows the T
The method for determining p and T is also illustrated. A baseline is drawn at a certain peak, and Tp and T, at that wavelength are determined as illustrated. Reference example 4 1 with stirring bar
000e reaction vessel, 18.5% by weight hydrochloric acid and 8.5% by weight
800k9 of a mixed aqueous solution at 18°C consisting of formaldehyde of % by weight was added, and the mixed aqueous solution was heated to 20°C while stirring.
36.4k9 of an aqueous solution of phenol containing % by weight of feathers at ℃ was added.

Pour the entire amount of the phenol aqueous solution. After stirring for (1) second, stirring was stopped and the mixture was allowed to stand for 2 hours. Eight and a half hours after the entire amount of the phenol aqueous solution was added, a sudden white cloudiness was observed in the reaction vessel, and the color gradually changed to a light pink color, and the internal temperature gradually rose to 34.5°C, and then dropped again. Then,
Reaction generation. While stirring the mixed aqueous solution system again, open the valve attached to the bottom of the reaction vessel to take out the contents, and use a Nomex nonwoven fabric to separate the reaction product and the mixed aqueous solution consisting of hydrochloric acid and formaldehyde. separated. The reaction product thus obtained was washed with water, dehydrated, immersed in a 0.5 wt% ammonia aqueous solution at 18°C for a day and night, and then washed again with water and dehydrated to obtain 44.6 kg of a reaction product with a water content of 15 wt%. Reaction product 2 obtained by the above method
．． 0k9 was dried at a temperature of 40℃ for 3 hours to obtain a sample of 1.7k.
g (Run No. 47). Table 5 shows 0.1 to 50μ and 0.1μ to 0.1μ by microscopic observation of the dried sample thus obtained.
Content of 1 to 100 micron particles, amount passed through a 100 taylor mesh sieve (100 mesh bath), 990 to 1015c71-1 and 890c by infrared absorption spectroscopy! The absorption wavelength intensity ratio (IR intensity ratio) of n-1 to 1600 cm-1 and methanol solubility are shown.

Example 1 The product of RunNO12 (as filler) 100y and RunNO. The resol resin (uncured product, 100 y in terms of prison sentence) used in 2 liters was mixed.

The obtained side fat mixture was dried at room temperature for a day and night, and then dried for 3 hours in an open dryer at 80°C. A certain amount of the obtained material was processed for 3 minutes under a pressure of 200 k9/cm using a mold preheated to 150°C, and the dimensions were 2 in width.
0? , 5 molded products each having a thickness of 3wn1 and a length of 120Tm were created. As a control product and as a filler, RunNO. 2
l, R immediate NO. 22, Run NO. The product obtained in 23 (
Cured product), wood powder, carbon black, and silica powder each passed through a 100-meter mesh sieve, R
unNO. Mix equal amounts of each with the resol resin used in 2L, and use the same method as described above to make the dimensions of the various fillers and resol resin 20cm wide, 3WrIn1 thick, 1L long.
Five molded products (precursors) each having a length of 20 m were created.

Next, these precursors were heated from room temperature to 10% under nitrogen gas flow.
The temperature was raised to 00°C at a rate of 30°C/hour, and then
The temperature was maintained at 000°C for 6 days. Thereafter, it was slowly cooled to obtain a carbonized fired product (carbon compact). Table 6 shows the type of filler used, the length retention rate of the carbonized fired product (relative to the precursor), the carbonization yield (relative to the precursor), the Vickers hardness,
Gas permeability and bending strength were shown. In Table 6,
Run NO. 52, Run NO. 53 and RurlN
O. All of the carbonized and fired products No. 55 had cracks and/or gas blisters, were bent, and were broken, making it difficult to measure the length retention rate.

In addition, there is a large variation in hardness. Example 2 Product of RunN0.42 (as filler) and Run
No. The resol resin (uncured product) used in 2l was mixed in various proportions to prepare (Run NO. 6l to Run NO. 68).
) The sample was air-dried at room temperature for 2 hours, and then dried at a temperature of 60°C for 6 minutes.

Approximately 50y of each sample was sown into 300k9 pieces using a mold preheated to 150°C in a heating press machine.
Two powders are processed under pressure of Clt, and the dimensions are width 13Trm1
Thickness 3.2~3.4T! r! A molded article having n1 length of 10 h and 10 fW1 of each sample was obtained. Next, these molded products (precursors for carbonization firing) were heated from room temperature to 100°C in 3 steps under nitrogen gas flow, held at 100°C for 3 days, and heated again to 1500°C. It took (a) time to raise the temperature to 1500°C, and then the temperature was maintained at 1500°C for 2 hours. Further, while continuing to flow nitrogen gas, the sample was left to cool for 12 hours, and the carbonized and fired sample (carbonized and fired product) was taken out. Table 7 shows Run NO. 6l~Run NO. RurlNO.68 in experiment. The mixing ratio of the product of No. 42 and the resol resin (in terms of solid content), the appearance and specific gravity of the precursor, the number of carbonized and fired products with no noticeable cracks or gas blisters (non-defective products), and the number of non-defective products. Specific gravity measured using
The carbonization yield, bending strength and electrical resistivity were shown.

Furthermore, RUI1NO. Since I couldn't get a good product for 6l,
Only specific gravity and carbonization yield are shown.

In addition, a glass-like luster was observed on the fractured surface of each carbonized and fired product, and the X-ray diffraction pattern had a broad peak near 23 and 24.

Example 3 4 parts by weight of the product of RUT1N0.35 (as filler) and Run NO. The resol resin used in 2l (
Four pots of precursor samples each consisting of 6 weighing parts (uncured product, solid content equivalent) were prepared in the same manner as in Example 2.

Five samples each were heated from room temperature to four times under a flow of helium gas.
3500C (Run NO. 7l) at a rate of 0°C/hour,
450℃ (Run No. 72), 5500C (Run No. 72)
No. 73), 6500C (Run NO. 74), 80
0°C (Run No. 75), 1000°C (Run No.
O. 76), 1500°C (Run No. 77), 180
00C (RLlrlrl!0.78) or 2,100
The temperature was raised to .degree. C. (Rllrl NO.79), maintained at each temperature (carbonization temperature) for 3 hours, and then allowed to cool. Table 8 shows the carbon content, specific gravity, bending strength, electrical resistivity, and X-ray diffraction angle of each carbonized and fired product obtained by elemental analysis.

Example 4 5 parts by weight of the product of RUI1N0.34 (as filler) and Run NO. The resol resin (uncured product) used in 2L, Run NO. The novolak resin obtained in No. 22 (containing 10% by weight of hexamethylenetetramine), Run NO.
44 product (thermal adhesive product), Run NO. 47 product (thermal adhesive product), furan resin (Hitafuran-303;
Hitachi Chemical Co., Ltd.), epoxy resin (Epicoat 815
; Shell Chemical Co., Ltd.) or coal tar pitte (softening point 125°C, quinoline insoluble matter 13.6%; Allied Chemical Co., Ltd.) was used in the method of Example 2, using 5 parts each in terms of solid content. Mixtures of various compositions were obtained.

Next, 2.5g of mixtures of various compositions were colored per sample and molded according to Example 2, and the dimensions were 13Tmt in width and 10Tm in thickness.
Ten 0Tfrm molded products (precursors) were obtained.

The precursor obtained by the above method was heated gradually from room temperature to 1000°C over two hours while flowing nitrogen gas, and then heated to 1000°C.
After maintaining the temperature for 60 minutes, it was allowed to cool. Table 9 shows the types of resin used and 10 samples each obtained by carbonization firing.
Number of items with no cracks or gas blisters (good items)
The carbonization yield and bending strength of a good product were shown.

Example 5 Early NO. 36 product, 100 tyler mesh powder of coconut shell powder, 100 tyler mesh flour, pulverized after heat treatment at a temperature of 500° C. under nitrogen atmosphere, 1
00 Tyler mesh pass polyvinyl alcohol or 100 Tyler mesh pass 4 parts each of silica powder and Rurl NO. 43 products (RunNO.9l-RunNO,
95) or Run NO. 43 product (Ru
NNO, 96) alone was extruded into a rope of 2 to 3 φ from a small extruder (manufactured by Sumitomo Heavy Industries, Ltd., type: 4) at a temperature of 150°C.

After that, the pieces were cooled in water and cut into lengths of about 10wn.
It was dried at a temperature of 0° C. for 5 hours to obtain a precursor for carbonization and firing. The above precursor was then heated from room temperature to 90°C while continuing to feed steam-containing nitrogen passed through hot water at 80'C.
The temperature was raised to a temperature of 00°C for 6 powders, and then kept at a temperature of 900°C for 3 powders, then cooled and taken out.

The first cough includes the type and composition of the raw materials used, the carbonization yield of the carbonized and fired product (relative to the precursor), the apparent density, the specific surface area by the BET method (N2 method), and the saturated adsorption amount of benzene at 20°C. showed that.

[Brief explanation of drawings]

FIG. 1 of the accompanying drawings is an infrared absorption spectrum diagram of an example of a granular or powdery phenol formaldehyde resin used in the present invention.

Claims (1)

[Scope of Claims] 1 (A) contains spherical primary particles and secondary aggregates with a particle size of 0.1 to 150 microns, and (B) has an absorption of 1600 cm^-^1 in the infrared absorption spectrum by the KBr tablet method. Strength is D_1_6_0_
The maximum absorption intensity in the range of 0,990 to 1015 cm^-^1 is D_9_9_0 to_1_0_1_5,890
If the absorption intensity of cm^-^1 is D_8_9_0,
D_9_9_0～_1_0_1_5/D_1_6_0_
0=0.2=0.9, D_8_9_0/D_1_6_0
A thermoformable resin composition containing at least a granular or powdered phenol-formaldehyde resin, or a thermoformable product of the granular or powdered phenol-formaldehyde resin, which exhibits _0 = 0.09 to 1.0. 1. A method for producing a carbon molded body, which comprises thermoforming a precursor molded body alone, and then carbonizing and firing the precursor molded body. 2. The method according to claim 1, wherein at least 30% of the granular or powdered resin comprises spherical primary particles and secondary aggregates thereof having a particle size of 0.1 to 150 microns. 3 The granular or powdered resin has an infrared absorption spectrum of D_9_9_0=_1_ by the KBr tablet method.
The method according to claim 1 or 2, wherein 0_1_5/D_1_6_0_0 is 0.3 to 7.0. 4 The granular or powdered resin has an infrared absorption spectrum of D_8_9_0/D_1 according to the KBr tablet method.
The method according to any one of claims 1 to 3, wherein _6_0_0 is 0.1 to 0.9. 5. The method according to any one of claims 1 to 4, wherein at least 50% by weight of the granular or powdered resin has a size that allows it to pass through a 100-meter mesh sieve. 6 The granular or powdered resin has a free phenol content of 500 ppm as measured by liquid chromatography.
The method according to any one of claims 1 to 5, which is less than or equal to m. 7 The granular or powdered resin practically consists of carbon, hydrogen and oxygen according to elemental analysis values, and has the following composition C: 70
-80% by weight, H: 5-7% by weight, and O: 17-21% by weight (total 100% by weight). 8. The granular or powdered resin is at least partially fused when held at a temperature of 100°C for 5 minutes according to the thermal fusion measurement method described in the main text. The method according to any one of items 1 to 7. 9 When 10 g of the granular or powdered resin is heated under reflux in 500 ml of substantially anhydrous methanol, the following formula S=[W_0-W_1]/W_0×100, where W_0 is the amount of water used The weight of the resin (g), W_1 is the weight (g) of the resin remaining after heating and refluxing, S is the methanol solubility of the resin (wt%), and the methanol solubility represented by is 20 wt% or more, patent The method according to any one of claims 1 to 8. 10 Claims 1 to 7, wherein the granular or powdered resin does not substantially melt or fuse when held at a temperature of 100°C for 5 minutes according to the thermal fusion measurement method described in the main text. The method described in any of the paragraphs. 11 When the thermoformable particulate or powdered phenol-formaldehyde resin alone is held at a temperature of 100°C for 5 minutes according to the heat fusion measurement method described in the text, at least a portion of it is fused. or by heating it to a temperature of 100°C for 5 minutes according to the same thermal fusion measurement method.
2. A method according to claim 1, which does not substantially melt or fuse when held for minutes. 12 At a temperature of 100°C according to the heat fusion measurement method described above,
It consists of a material that at least partially fuses when held for a minute and a material that does not substantially melt or melt, and the above-mentioned material that is at least partially fused accounts for at least 10% by weight of the whole.
12. The method of claim 11, wherein the method comprises: 13. The method according to claim 1, wherein the thermoformable resin composition further contains other carbonized materials in addition to the granular or powdered phenol-formaldehyde resin. 14. The method of claim 13, wherein the carbonized material is a first carbonized material that is a curable resin. 15. The method of claim 14, wherein the first carbonized material is a thermosetting resin. 16. The method according to claim 15, wherein the thermosetting resin is a resol resin, a novolak resin, an epoxy resin, a furan resin, a melamine resin, or a urea resin. 17. The method according to claim 13, wherein the carbonized material is a second carbonized material selected from coke, anthracite, caking bituminous coal, pitch, or a cured product of a thermosetting resin. 18 The carbonized material is a carbohydrate, a carbohydrate derivative,
or the second carbonized material selected from natural products containing carbohydrates as a main component. 19. The method of claim 18, wherein the carbohydrate is cellulose, starch or sugar. 20. The method according to claim 13, wherein the carbonized material is a third carbonized material selected from thermoplastic resins and thermoinfusible resins other than cured products of curable resins. 21. The method according to claim 20, wherein the thermoplastic resin is polyamide, polyvinyl acetate, vinyl chloride, vinylidene chloride or polyacrylonitrile resin. 22 Claim 20, wherein the heat-infusible resin is polyvinyl alcohol or polyvinyl formal.
The method described in section. 23. The method of claim 1 or 13, wherein the thermoformable resin composition further contains an inorganic filler. 24. The method of claim 23, wherein the inorganic filler is silica, alumina, silica-alumina, calcium carbonate, calcium silicate, or a noble metal. 25 The thermoformable resin composition comprises (a) a granular or powdered phenol formaldehyde resin, (b) a curable resin (first carbonized material), and/or (c) the second or third carbonized material. consisting of a carbonized material or an inorganic filler, the granular or powdered resin of (a) above is at least 10% by weight of the total composition, and the granular or powdered resin of (a) above is thermoformable; 2. A method according to claim 1, wherein the amount of the second carbonized material of (b), alone or in total, is at least 20% by weight of the total composition. 26 The granular or powdered resin of (a) above is at least 20% by weight of the total composition, and the granular or powdered resin of (a) above is thermoformable and/or (
26. The method of claim 25, wherein the amount of the second carbonized materials of b), alone or in total, is at least 30% by weight of the total composition. 27 The granular or powdered resin of (a) above is at least 30% by weight of the total composition, and the granular or powdered resin of (a) above is thermoformable and/or (
27. The method of claim 26, wherein the amount of the second carbonized materials of b), alone or in total, is at least 40% by weight of the total composition. 28. The method of any of claims 1 to 27, wherein the carbonization calcination is carried out at a temperature of about 450°C or higher. 29. The method of claim 28, wherein said carbonizing calcination is carried out at a temperature between about 500 and about 2500<0>C. 3
0. The method according to any one of claims 1 to 29, wherein the carbonization firing is performed in a non-oxidizing atmosphere. 31. The method of claim 30, wherein the non-oxidizing atmosphere is substantially free of molecular oxygen. 32. The method according to claim 30 or 31, wherein the non-oxidizing atmosphere contains at least one selected from nitrogen, helium, hydrogen, and carbon monoxide as a main atmospheric gas. 33. The method according to any one of claims 1 to 29, wherein the carbonization firing is performed in an atmosphere containing hydrogen gas or carbon dioxide.