JPS6132247B2 - - 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 powdery compound 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. This invention relates to a method for producing a carbon molded article with excellent strength and high hardness using nitrogen phenol aldehyde resin. Conventionally, novolac resins and resol resins are known as typical phenolic aldehyde resins. Novolac resins usually have a molar ratio of phenol to formaldehyde, e.g. 1:0.7.
Under conditions of phenol excess such that ~0.9;
In the presence of an acid catalyst such as oxalic acid (usually 0.2
-2%) by reacting phenol with formalin. The novolac resin obtained by such a method is mainly composed of trimers to pentamers of phenols bonded mainly through methylene groups, contains almost no free methylol groups, and therefore cannot self-react by itself. It has no crosslinking properties and is thermoplastic. Therefore, the novolac resin is reacted under heat with a crosslinking agent which is itself a formaldehyde generator and also an organic base (catalyst) generator, such as hexamethylenetetramine (hexamine), or with a solid acid catalyst and 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 cured 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 remove the solvent and mold the product using a filling material, but when such molded products are subjected to carbonization firing, gas blisters and cracks occur, similar to the case with the novolac resins mentioned above. It is very difficult to produce carbon molded bodies of satisfactory quality in terms of strength or hardness. In addition, in relatively recent years, novolak resins have been heated at high temperatures to obtain products with a fairly high degree of condensation, and this has been purified to separate and remove low condensates, resulting in phenol groups containing 7 to 10 methylene 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 novolak resin fibers was proposed by proceeding the curing reaction from the outside of the fibers (Japanese Patent Publication No. 1983-1999).
No. 11284). However, cutting or crushing the cured novolac 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 of producing a carbon molded article from a composition of the above-mentioned cured novolak resin fibers and other carbonized materials has also been recently proposed (see Japanese Patent Application Laid-open No. 77293/1983). 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, a hydrophilic polymer compound is added to a condensate obtained by reacting phenols and formaldehyde in the presence of at least a nitrogen-containing compound, and the reaction is performed to produce granular or powdered resin. Although a method has been announced (Special Publication 1973-
42077), the non-gelled resin obtained by this method contains a large amount of free phenol, approximately 5-6% (Examples 1 to 4), and the gelled product (Example 5) is an extremely hard non-gelled product. Not only is it a reactive resin, but it also contains a hydrophilic polymer compound. Therefore, it not only deteriorates the performance of the molded product obtained by using it as a filler, but also has the drawback of causing cracks and gas blisters in the carbon molded product obtained from the molded product. 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), which corresponds to the so-called cured resol resin product, has no reactivity, and also contains salts, acids, and other protective colloids, so it can also be used as a filler for molded products. Not only does it reduce its performance, but it also has the drawback 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. First of all, it is difficult to obtain it, and it also has the problem of containing substances that have an undesirable effect on molded products, especially molded products for carbonization. The present inventors have previously provided a new granular or powdery nitrogen-containing phenol aldehyde resin that does not have the above-mentioned drawbacks and a method for producing the same. Therefore, an object of the present invention is to provide a method for producing a carbon molded body using a novel granular or powdery nitrogen-containing resin as a carbonized material. Another object of the present invention is a method for producing a carbon molded body having excellent strength and high hardness using a granular or powdery nitrogen-containing resin having good flow characteristics as a carbonized material. Our goal is to provide the following. Still another object of the present invention is to use a granular or powdered nitrogen-containing resin as a carbonization material to produce a precursor molded article (a molded article for carbonization) using the same.
An object of the present invention is to provide a method for producing a carbon molded body from a carbon material with a high carbonization yield. Still another object of the present invention is to use a granular or powdery nitrogen-containing resin that is reactive with itself or with other resins as a carbonization material, thereby reducing cracks and gas blisters and reducing internal damage. To provide a method for producing a precursor molded body with almost no unevenness in quality between the outside and the carbon molded body, and thus producing a carbon molded body having no cracks or gas blisters and having a homogeneous inside and outside. be. 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. Still another object of the present invention is to provide a nitrogen-containing carbon molded article having a high specific surface area. Further objects and advantages of the present invention will become apparent from the following description. The objects and advantages of the present invention are, according to the present invention, a granular or powdered resin comprising a phenol, a nitrogen-containing compound having at least two active hydrogens, and a condensate with an aldehyde, comprising: (A) The granular or powdered resin contains spherical primary particles with a particle size of 0.1 to 100 microns and secondary aggregates thereof, and (B) the infrared absorption spectrum of the resin by the KBr tablet method is in the range of 1450 to 1500 cm ^-1 When the largest absorption intensity in the range of _{960 to 1020} cm -1 is expressed as D 1450 _{to 1500} , and the largest absorption intensity in the range of 960 to 1020 cm ^-1 is expressed as D 960 to 1020, D _{960 to 1020} / D _{1450 to 1500} = 0.1 to 2.0. , a thermoformable resin composition containing at least granular or powdered nitrogen-containing phenolic aldehyde;
Or, by a method for producing a carbon molded body, which is characterized in that a precursor molded body is thermoformed from a thermoformable part of the granular or powdered nitrogen-containing phenol aldehyde resin, and then the precursor molded body is carbonized and fired. It will be achieved. Such granular or powdered nitrogen-containing phenolic aldehyde resins used in the present invention include phenols, or phenols containing at least 50% by weight of phenols, especially at least 70% by weight of phenols, such as o-cresol, m-cresol, p-cresol. Cresol, bis-phenol A, o-, m- or p-
A condensate of a mixture with one or more known phenol derivatives such as C ₂ to C ₄ alkylphenol, p-phenylphenol, xylenol, and resorcinol, and a nitrogen-containing compound having at least two active hydrogens and an aldehyde. includes. The granular or powdery nitrogen-containing resin in the resin composition of the present invention has the properties (A) and (B) described above. In specifying (A) and (B) above, (A) specifying that the particle size of the spherical primary particles and their secondary aggregates is 0.1 to 100 microns, (B) D _{960 ~ 1020} / D _{1450 ~} The specification of ₁₅₀₀ = 0.1 to 2.0 is based on the measurement method described later. The first feature of the granular or powdered nitrogen-containing resin is that it is extremely difficult to crush a conventionally known cured product of novolak resin or cured resol resin, but It is completely different from the known pulverized hardened novolac resin fibers, and as specified in (A) above, most of them are spherical primary particles and secondary aggregates thereof, with a particle size of 0.1 to 100 microns. things, preferably
Contains 0.1 to 50 microns. The above granular or powdered nitrogen-containing resin usually has at least 30%, preferably at least 50%, particle size.
It consists of spherical primary particles of 0.1 to 100 microns, more preferably 0.1 to 50 microns, and secondary aggregates thereof. This indication of 30% or 50% means that the magnification is 100 to 100%, as defined in the particle size measurement method described below.
It means 30% or 50% of the total number of particles (including secondary aggregates) in one field of view of a 1000x optical microscope. Particularly preferred is one in which 70 to substantially 100% of the granular or powdered nitrogen-containing resin consists of spherical primary particles and secondary aggregates thereof having a particle size of 0.1 to 100 microns. Particularly preferred is at least 30%, in particular at least 50% of the number of particles (as the average value of 5 fields) of the field of the optical micrograph according to the above definition.
The particles are comprised essentially 100% of spherical primary particles and secondary agglomerates thereof ranging from 0.1 to 50 microns, more preferably from 0.1 to 20 microns. As mentioned above, the above granular or powdered nitrogen-containing resin is formed mainly of the above spherical primary particles and microparticles of secondary aggregates thereof, so it is extremely small and has a small proportion of the total. A total of 50% by weight, preferably 70% by weight, particularly preferably at least 80% by weight of the total passes through a 150 sieve mesh. Such an indication that the granular or powdered product passes through the sieve may be indicated by gently kneading the granular or powdered product by hand, or by brushing the granular or powdered product with the sieve. Do not apply any force that does not forcibly destroy the particles (including secondary aggregates), such as lightly pushing or smoothing the particles on the sieve, or tapping them with your hand. It is not something to be excluded. The above granular or powdery nitrogen-containing resin further includes:
As specified in (B) above, in the infrared absorption spectrum, it has the following characteristics: D _960-1020 /D _1450-1500 = 0.1-2.0, and preferably, D _1280-1360 /D _1450-1500 = 0.15-3.0. . Further, the preferable granular or powdery nitrogen-containing resin used in the present invention is D _960-1020 / D _1450-1500 = 0.15-0.6, preferably further D _1280-1360 / D _1450-1500 = 0.2-2.0 Particularly preferred ones have the following characteristics: D _960-1020 /D _1450-1500 = 0.2-0.4, and more preferably, D _1280-1360 /D _1450-1500 = 0.3-1.5. Further, the granular or powdered nitrogen-containing resin used in the present invention further has the largest absorption intensity in the range of 1580 to 1650 cm ^-1 expressed as D _{1580 to 1650} in the infrared absorption spectrum by the KBr tablet method. D _{1580 ~ 1650} / D _{1450 ~ 1500} = 0.3 ~ 4.5 (preferably 0.75 ~ 2.0, particularly preferably 1.0 ~
1.5) It has the following characteristics in the infrared absorption spectrum. Generally, it is difficult to determine the attribution of various functional groups in a substance having a three-dimensional crosslinked structure using an infrared absorption spectrum. That is, this is because the peak in an infrared absorption spectrum diagram often shifts significantly. However, from the infrared absorption spectra of phenol aldehyde resins and various nitrogen-containing compounds, the above absorption in the infrared absorption spectrum of the present invention shows that the absorption at 960 to 1020 cm ^-1 is a peak belonging to the methylol group, and 1280 to 1360 cm ^-1 The absorption of is the peak attributed to the carbon-nitrogen bond, and 1450 ~
The absorption at 1500 cm ^-1 was determined to be the peak attributed to aromatic double bonds. Also, although it is difficult to clearly attribute the absorption of 1580 to 1650 cm ^-1 , the above ratio using the intensity of this absorption
The values of D _1580-1650 /D _1450-1500 indicate values that can clearly distinguish the ratio in phenol-formaldehyde resins that do not contain nitrogen, and therefore are similarly characteristic values for specifying the resin of the present invention. It can be recognized as absorption. One parameter for specifying the granular or powdery nitrogen-containing resin used in the present invention,
Ratio of the above absorption intensities in the infrared absorption spectrum, for example D _{960 ~ 1020} / D _{1450 ~ 1500} = 0.1 ~ 2.0
This range indicates that the nitrogen-containing resin used in the present invention contains a considerable amount of methylol groups,
Furthermore, it can be understood that the content of methylol groups can be adjusted within a certain range, indicating a characteristic value linked to the structure. The granular or powdered nitrogen-containing resin used in the present invention usually has a free phenol content of 500 ppm or less as measured by liquid chromatography, and more preferred products have a free phenol content of 300 ppm or less, especially 100 ppm or less. It is. The granular or powdered resin obtained by the method disclosed in Japanese Patent Publication No. 53-42077 contains an extremely large amount of free phenol, from 0.3 to about 6% by weight, whereas the granular or powdered resin used in the present invention The free phenol content of nitrogen-containing resins is extremely small. This fact provides an important advantage in use for this type of granular or powdered resin. It has also been found that many of the granular or powdered nitrogen-containing resins used in the present invention contain at least 1% by weight of nitrogen, preferably 2 to 30% by weight. The granular or powdered nitrogen-containing resin used in the present invention can 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. can. As a result, thermally, the granular or powdery nitrogen-containing resin used in the present invention has (a) It includes both (b) those in which at least a portion thereof is fused to form a lump or plate-like body, and (b) those that are not substantially melted or fused and take the form of granules or powder. When the solubility of the resin in (a) above, which has relatively high fusibility, is measured in methanol according to the test method described later, it is 20% by weight or more, even 30% by weight or more, and even more than 40% by weight. Included are resins that exhibit methanol solubility of . The granular or powdered resin used in the present invention is characterized by having the properties (A) and (B) described above. The granular or powdered nitrogen-containing resin used in the present invention has a particle size of 0.1 to 100 microns, preferably
Contains spherical primary particles of 0.1 to 50 microns and secondary aggregates thereof (condition (A) above), preferably at least 50% and usually at least 50% by weight, preferably at least 70% by weight. Weight% is 150
Since it has a size that allows it to pass through a Tyler mesh sieve, it has extremely good fluidity and can be easily mixed with other carbonized materials in a relatively large amount. Further, since at least many of the granular or powdery nitrogen-containing resins used in the present invention have extremely small spherical primary particles as a basic constituent, the thermosetting resin of the present invention containing these particles The cured moldings obtained by curing the composition exhibit excellent mechanical properties, in particular strong resistance to compression. The granular or powdered nitrogen-containing resin used in the present invention is extremely stable at room temperature, and since it itself contains a considerable amount of methylol groups, it exhibits reactivity when heated, and as shown in the examples below, it exhibits physical and A cured molded product is formed which has extremely excellent not only mechanical properties but also electrical properties such as heat insulation, heat resistance, electrical insulation, and chemical resistance. The granular or powdered nitrogen-containing resin used in the present invention further has a free phenol content of usually 500 ppm.
It is preferably as low as 300 ppm or less, especially 100 ppm or less. Since the phenol content is extremely low, the granular or powdered nitrogen-containing resin used in the present invention is extremely easy to handle and is safe. Further, since the granular or powdered nitrogen-containing resin used in the present invention has an extremely low free phenol content as described above, the side reaction rate due to phenols is reduced when a precursor molded body is obtained from it. In addition, the granular or powdered nitrogen-containing resin used in the present invention is usually hydrophilic because it is produced by a production method that does not substantially contain a hydrophilic polymer compound in the reaction system, as is clear from the production method described below. Contains substantially no polymeric compounds. As mentioned above, the granular or powdered nitrogen-containing phenol/aldehyde copolymer resin used in the present invention is extremely fine, has good storage stability and flow characteristics, and contains a certain amount of methylol groups, so it is difficult to use as a precursor. Since it is reactive when a molded body is molded and heated, it has the excellent feature of providing a carbon molded body with uniform physical properties. The granular or powdered resin used in the present invention has (1) the following composition (a) a hydrochloric acid (HCl) concentration of 3 to 28% by weight, and (b) a formaldehyde (HCHO) concentration of 3 to 28% by weight.
25% by weight and the concentration of aldehydes other than formaldehyde is 0 to 10% by weight, and (c) the total concentration of hydrochloric acid and formaldehyde is 10 to 10% by weight.
(2) A phenol and a nitrogen-containing compound having at least two active hydrogens are added to a hydrochloric acid-almaldehyde bath of 40% by weight according to the following formula (), bath ratio = weight of the above hydrochloric acid-formaldehyde bath/ It can be produced by contacting them while maintaining the bath ratio represented by the weight of the phenols + the weight of the nitrogen-containing compound to be at least 8 or more. As for the composition of the hydrochloric acid-formaldehyde bath in (1) above, in addition to the three conditions (a), (b), and (c) above, the additional condition (d) is formaldehyde (mol) in the bath/ It is preferable that the total molar ratio of phenols (moles) and nitrogen-containing compounds (moles) in contact with the nitrogen-containing compound be at least 2 or more, particularly 2.5 or more, especially 3 or more. The upper limit of the molar ratio in the above condition (d) is not particularly limited, but it is preferably 20 or less. The upper limit of the molar ratio in the above condition (d) is not particularly limited, but is 20 or less, especially
15 or less is suitable. The above molar ratio is particularly 4 to 15,
Of these, 8 to 10 are preferred. The characteristics of the above manufacturing method are:
As described above, a bath of a hydrochloric acid-formaldehyde aqueous solution having a fairly high concentration of hydrochloric acid (HCl) and an excess of formaldehyde relative to phenols and nitrogen-containing compounds is prepared at a bath ratio of 8 or more, preferably 10.
The purpose is to contact the phenols and nitrogen-containing compounds at such a large ratio. That is, to explain further, the above method is carried out under the conditions that the respective concentrations of hydrochloric acid and formaldehyde are 3% by weight or more and the bath ratio is 8 or more, so that the total weight of phenols and nitrogen-containing compounds is The weight proportions of both hydrochloric acid and formaldehyde to the total amount of water are at least 24% by weight.
Furthermore, since the above method is carried out at a total concentration of hydrochloric acid and formaldehyde of 10% by weight or more, the total weight of hydrochloric acid and formaldehyde relative to the total weight of phenols and nitrogen-containing compounds is 80% by weight or more. As mentioned above, such reaction conditions are fundamentally different from the reaction conditions for producing novolac resins and resol resins known in the art. When the phenols and the nitrogen-containing compound are brought into contact with the hydrochloric acid-formaldehyde bath, the bath ratio represented by the above formula () is preferably 10 or more, particularly 15-40. The phenols and the nitrogen-containing compound are brought into contact with the hydrochloric acid-formaldehyde bath in such a way that after the phenols come into contact with the bath, a white turbidity is formed, and then a granular or powdery solid is formed. The contact between the hydrochloric acid-formaldehyde bath and the phenols and nitrogen-containing compounds can be carried out by adding the phenols and the nitrogen-containing compound together into the hydrochloric acid-formaldehyde bath, or by adding the nitrogen-containing compound and then adding the phenol. It is preferred to first form a clear solution, then to form a cloudy cloud, and then to form a granular or powdery solid.
At this time, before adding phenols to the bath to generate cloudiness, the bath is stirred so that the added phenols and nitrogen-containing compounds form a transparent solution as uniform as possible. Depending on the ratio of phenols and nitrogen-containing compounds and the reaction conditions, the bath (reaction liquid) may be subjected to mechanical shearing force such as stirring during the period from the time when cloudiness occurs until solid matter is formed. It is preferable not to give The phenol to be added may be the phenol itself, or may be a phenol diluted with formalin, an aqueous hydrochloric acid solution, water, or the like. Furthermore, when adding phenols or phenols and nitrogen-containing compounds (or diluted solutions thereof), the temperature of the hydrochloric acid-formaldehyde bath or the temperature of the hydrochloric acid-formaldehyde bath in which the nitrogen-containing compound has been dissolved in advance is 90°C. Below, a temperature of 70°C or lower is particularly suitable. If the temperature of the bath is higher than 40°C, especially higher than 50°C, the reaction rate between phenols and nitrogen-containing compounds and formaldehyde will be high, so phenols or phenols and nitrogen-containing compounds should not be used. It is preferable to add it to the bath as a dilute solution diluted with the formalin solution. In this case, since the reaction rate is high, the phenols, or the phenols and the nitrogen-containing compound, are added to the bath and brought into contact, especially in the form of a trickle of a diluted solution thereof or as fine droplets as possible. is preferable. When the bath temperature is 40°C or higher, especially 50°C or higher, when phenols, phenols and nitrogen-containing compounds, or diluted solutions thereof are brought into contact with this bath, the higher the bath temperature, the higher the temperature. The reaction rate between the phenols and the nitrogen-containing compound increases, and after the contact, white turbidity is formed within a short time or instantaneously within a few minutes, and granular or powdery solids are rapidly formed. Keep the temperature of the hydrochloric acid-formaldehyde bath below 40℃.
Preferably 5° to 35°C, particularly preferably 10 to 30°C
Add the phenols and the nitrogen-containing compound as they are or the diluted solution thereof, preferably a water-diluted solution of the phenol and the nitrogen-containing compound, to this bath, and after the formation of white turbidity, add the phenols and the nitrogen-containing compound to this bath.
For granular or powdered solids that have completed the desired reaction at a temperature of 45°C or lower, the curing reaction has not progressed sufficiently, so they generally exhibit thermal fusion properties in the thermal fusion measurement method described below. . On the other hand, the temperature of the hydrochloric acid-formaldehyde bath was set to 40
℃ or less, preferably 15° to 35° C., add the phenols and nitrogen-containing compounds to be added to the bath as they are or substantially the entire amount of the diluted solution thereof under stirring to form a transparent solution, After that, white turbidity is generated in a non-stirring state, and then a pale pink granular or powdery solid is generated without increasing the temperature, and this solid is heated at a temperature higher than 50°C.
Preferably, when the desired reaction is completed by heating to a temperature of 70° to 95°C, the curing reaction progresses more, so the thermal fusion properties at 100°C measured by the thermal fusion measurement method described below will be lowered or or exhibits heat-fusibility at higher temperatures, such as 200° C., or exhibits substantially no heat-fusibility even at such high temperatures. In any of the above cases, it is also possible to add the nitrogen-containing compound to the hydrochloric acid-formaldehyde bath in advance and then add only the phenols. As the phenol used in the above method, phenol is most suitable, but as long as it contains at least 50% by weight of phenol, especially at least 70% by weight, o-cresol, m-cresol, p-cresol, etc.
It may be a mixture with one or more of known phenol derivatives such as cresol, bis-phenol A, o-, m- or p- _C2 - _C4 alkylphenol, p-phenylphenol, xylenol, resorcinol, etc. . The nitrogen-containing compound used in the above method is a compound having at least two active hydrogens in the molecule, preferably an amino group having active hydrogen in the molecule,
A compound having at least one group selected from the group consisting of an amide group, a thioamide group, a urein group, and a thiouraine group is used. Examples of such nitrogen-containing compounds include urea,
Examples include thiourea, urea or methylol derivatives of thiourea, aniline, melamine, guanidine, guanamine, dicyandiamide, fatty acid amide, polyamide, toluidine, cyanuric acid, or functional derivatives thereof. These can be used alone or in combination of two or more. The granular or powdered solid nitrogen-containing phenol aldehyde resin produced in the bath as described above and having completed the desired reaction is separated from the hydrochloric acid-formaldehyde bath, washed with water, and preferably The desired product can be obtained by neutralizing the hydrochloric acid with an alkaline aqueous solution, such as aqueous ammonia or methanolic aqueous ammonia, and further washing with water. In this case, as a matter of course, if the resin has a relatively high methanol solubility, it is preferable to neutralize it with an aqueous alkaline solution. The method of the present invention is carried out by first producing a precursor molded body by thermoforming from the granular or powdered nitrogen-containing phenol aldehyde resin alone or a resin composition containing at least the granular or powdered nitrogen-containing resin. . Naturally, the granular or powdered nitrogen-containing phenolic aldehyde resin or the resin composition used alone must be thermoformable. Therefore, the granular or powdery nitrogen-containing phenol aldehyde resin used alone is
The nitrogen-containing phenol aldehyde resin of (a) above or the nitrogen-containing phenol aldehyde resin of (a) above, which 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 nitrogen-containing phenol-aldehyde resin (b) that does not substantially melt or fuse according to the same thermal fusion measurement method as the nitrogen-containing phenol-aldehyde resin is preferably used. In the case of the latter (mixture), the nitrogen-containing phenol-formaldehyde resin (b) acts as a filler and the nitrogen-containing phenol-aldehyde resin (a) acts as a binder in the precursor molding. In the case of the above-mentioned resin composition containing a granular or powdered nitrogen-containing phenol-aldehyde resin, the nitrogen-containing phenol-aldehyde resin does not necessarily contain at least one part of the resin according to the thermal fusion measurement method.
It does not need to be (a) or a mixture of (a) and (b) in which the parts are fused. That is, as long as the resin composition contains, in addition to the granular or powdered nitrogen-containing phenol-aldehyde resin, a binder that enables thermoforming due to its presence, the granular or powdered nitrogen-containing phenol-aldehyde resin It does not need to be fusible (a). In other words, if a granular or powdered nitrogen-containing phenol aldehyde resin is present with another resin that can act as a binder, even if it is fusible (a), it is not meltable or fusible (a). b) is used in exactly the same way. As is clear from the foregoing, what is important in the present invention is that the granular or powdered nitrogen-containing phenol aldehyde resin is used as a component of the precursor molded body, and that the resin is used in the precursor molded body. It's not really a filler or a binder. Whether the granular or powdered nitrogen-containing phenol aldehyde of either (a) or (b) is fusible (a) or not (b) must be considered when manufacturing the precursor molded body. No matter which resin is used, carbon molded bodies with excellent strength and hardness can still be obtained through carbonization and firing. In the method of the present invention, the precursor molded body is made of a granular or powdered nitrogen-containing phenol aldehyde resin alone, and the granular or powdered nitrogen-containing resin has a fusibility and does not have fusibility. things (b)
If it is a mixture with
(a) is at least 10% by weight, more preferably 20% by weight of the total
% by weight, especially 30% by weight. In the method of the present invention, the resin composition containing at least a granular or powdered nitrogen-containing phenol-aldehyde resin may further contain other carbonized materials in addition to the granular or powdered nitrogen-containing phenol-aldehyde resin. . The carbonized material may be a curable resin (first carbonized material). Thermosetting resin is preferred as the first carbonized material. For example, resol resins, novolak resins, epoxy resins, furan resins, melamine resins or carbon resins are preferably used. These carbonized materials can act as binders, so when using such carbonized materials, the granular or powdered nitrogen-containing phenol aldehyde resin used together must have fusibility (a). It may also be (b), which does not have any Any granular or powdered nitrogen-containing phenol
Even when it comes to aldehyde resins, these resins are grown by the reaction of cloudy microparticles, which are the initial reaction products of phenols, with formaldehyde, so they have a high carbon content and are extremely stable at room temperature. Moreover, since it itself contains a considerable amount of methylol groups, it shows reactivity when heated, and provides a precursor that is integrated with the first carbonized material. Furthermore, since the granular or powdered nitrogen-containing phenol aldehyde resin used in the present invention is extremely fine and has a large surface area as described above, it is easy to uniformly disperse it with the first carbonized material. Therefore, even when used in a relatively small amount, a carbon molded body with a high carbonization yield, excellent airtightness, and no gas blisters can be obtained by carbonization firing. The fact that the granular or powdered nitrogen-containing phenol aldehyde 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, the precursor molded body becomes a cured resol resin. When the carbonization yield is 50 to 54% by weight, the precursor molded body consists of the above granular or powdered nitrogen-containing phenol aldehyde resin alone, or 50 parts by weight (as solid content) of the resol resin and the above granular or powdery nitrogen-containing phenol aldehyde resin. This is clear from the fact that when the mixture is composed of a mixture with 50 parts by weight of a powdered nitrogen-containing phenol aldehyde resin, the carbonization yield is 60 to 70% by weight. The carbonization yield is 54 to 58% by weight when the granular or powdered nitrogen-containing phenol aldehyde resin used in the present invention is carbonized at the same temperature without using it as a precursor molded body. Taking this into consideration, the granular or powdered nitrogen-containing phenol aldehyde resin used in the present invention has reactivity by itself and with other resins, so it can be molded into carbon from a precursor molded body with a high carbonization yield. It is believed that it gives the body. When the first carbonized material is mixed with the granular or powdered nitrogen-containing phenol aldehyde resin and thermoformed to produce a precursor molded body, which is carbonized and fired, the precursor molded body made only of the carbonized material is carbonized. It can be said that a carbon molded body can be obtained with a higher carbonization yield than when fired. The carbonized material used in the resin composition is further
It can also be a carbonized material. As the second carbonized material, for example, 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 nitrogen-containing phenol aldehyde 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 it can provide a high carbonization yield. coke,
Anthracite and cured thermosetting resins can be used as fillers, pitch can be used as binders, and caking bituminous coal can be used 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 mainly composed of carbohydrates, such as carbohydrates such as cellulose (rayon), starch, and sugar, carboxymethyl cellulose, hydroxyethyl cellulose, and acetyl cellulose. carbohydrate derivatives such as or wood flour,
Natural products mainly composed of carbohydrates such as linters, coconut shells, rice hulls, and grain flours; secondly, thermoplastic resins such as polyamides, polyvinyl acetates,
Vinyl chloride, vinylidene chloride or polyacrylonitrile resins, or heat-infusible resins other than cured products of curable resins, such as polyvinyl alcohol or polyvinyl formal, are preferably used. The above-mentioned third carbonized material generally has a low carbonization yield, and the carbon molded body obtained by carbonizing and firing a precursor molded body using the third carbonized material provides voids and often has voids with an activated inner wall. give. 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 nitrogen-containing phenol aldehyde resin may further contain an inorganic filler independently of the carbonized material. Unlike the above-mentioned 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 when improving the situation. For example, silica, alumina, silica-alumina, calcium carbonate, calcium silicate, or noble metals such as gold, silver, palladium, platinum, etc. can be mentioned. 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, the resin composition containing at least a granular or powdery nitrogen-containing phenol-aldehyde resin comprises (i) a granular or powdery nitrogen-containing phenol-aldehyde resin and (ii) a curable resin (a first carbonized material) and/or (iii) the second or third carbonized material or inorganic filler. In the method of the present invention, when the precursor molded body is made of the resin composition, the granular or powdered nitrogen-containing phenol aldehyde resin accounts for at least 10% by weight of the total composition, and the granular or powdered nitrogen-containing phenol aldehyde resin The thermoformable nitrogen-containing phenolic aldehyde resin (resin (a) above) and/or the second carbonized material alone or in total may account for at least 20% by weight of the total composition. preferable. More preferably, the granular or powdered nitrogen-containing phenolic aldehyde resin accounts for at least 20% by weight of the total composition, and the thermoformable granular or powdered nitrogen-containing phenolic aldehyde resin and/or
or the second carbonized materials alone or in combination account for at least 30% by weight of the total composition. In particular, the granular or powdery nitrogen-containing phenolic aldehyde resin accounts for 30% by weight of the total composition, and the thermoformable granular or powdery nitrogen-containing phenolic aldehyde resin and/or the second carbonized material It is particularly preferred that the amounts alone or in total represent at least 40% by weight of the total composition. As described above, in the method of the present invention, a precursor molded body is first produced by thermoforming from a granular or powdered nitrogen-containing phenol-aldehyde resin alone or a resin composition containing at least a granular or powdered nitrogen-containing phenol-aldehyde 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 a granular or powdered nitrogen-containing phenol aldehyde resin alone, the temperature must be at least at least the melting temperature of the component (a) to be fused (for example, about 50 to about 200 °C). ℃),
In the case of the above-mentioned resin composition, the temperature is at least higher than the temperature at which the binder component therein melts (for example, about
100 to about 150[deg.] C.) and may be heated and pressurized into a desired shape by a method known per se, such as injection molding, press molding, or mold molding. All of these thermoforming methods involve external heating, but
According to the present invention, since a granular or powdery nitrogen-containing phenol aldehyde resin is used which is reactive with itself or with other resins and has very small particles and a large surface area, the granular or powdery nitrogen-containing phenol aldehyde resin is used. Not only when nitrogen phenol/aldehyde 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 the obtained precursor molded body is substantially free from the inside. It is hardened uniformly and does not generate decomposition gas that would cause cracks or gas blisters in the carbon molded body 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 interior 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. Carbonization firing is preferably carried out at a temperature of about 450°C or higher,
More preferably, it is carried out at a temperature between about 500 and about 2500°C. Furthermore, carbonization firing is carried out under a non-oxidizing atmosphere, usually an atmosphere that does not substantially contain molecular oxygen, for example, containing at least one selected from nitrogen, helium, hydrogen, and carbon monoxide as the main atmosphere gas. Perform under atmospheric conditions. An appropriate temperature increase rate when performing carbonization firing differs depending on the thickness or airtightness of the precursor molded body.
Generally, it is desirable to raise the temperature more slowly as the thickness and airtightness of the precursor molded body increases. The heating rate ranges from about 10°C/hour to about 2000°C/hour. The temperature and atmosphere of carbonization firing have a considerable influence on the properties of the obtained carbon molded body. For example, when carrying out carbonization firing at a temperature of about 700° to about 1000°C in an atmosphere of water vapor, carbon dioxide, a mixture of these, or a mixture of these and the above-mentioned non-oxidizing gases, the specific surface area is relatively small. A large carbon molded body is obtained. In addition, for example, the conditions when carrying out carbonization firing at a temperature of about 500° to about 800°C are suitable for producing a carbon molded body with conductivity in the range of semiconductors;
The conditions in which the temperature is about 2000° C. are suitable for producing a highly conductive carbon molded body suitable for heat exchanger pipes, 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 was confirmed by the presence of a broad peak around the diffraction angle (2θ) of 23 to 24 degrees in the X-ray diffraction diagram. 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 nitrogen-containing phenol aldehyde resin, especially one that does not melt or fuse (b), and another resin that serves as a binder. The resulting 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, abrasion resistance,
Indicates sliding properties or chemical resistance. Therefore, the carbon molded article obtained by the method of the present invention is
For example, sliding materials such as bearings, gears, bearings, aircraft brakes, motor brushes; heat exchangers,
Corrosion-resistant materials such as Raschig rings and bubbler catalyst carriers; Heaters such as heaters for electronic devices and solar house heaters; Insulating materials such as insulation plates for vacuum furnaces and protective tubes for high-temperature furnaces; For caustic soda, fuel cells, and scouring Electrodes for use; electricity such as semiconductors and radio wave reflecting gas;
It can be suitably used for electronic parts, etc. In addition, it has excellent strength, hardness, and wear resistance, so it can be used, for example, as typesetting or abrasive grains; because it has excellent chemical resistance, it can be used, for example, as aggregate for living organisms, analytical instruments, or ceramic/glass processing. It can also be used as a jig. Furthermore, those that have a large specific surface area or contain catalytic metals or have been added through post-processing, such as filters such as air filters, ozone filters, water filters, and oil filters; car canisters; and adsorbents for solvent recovery equipment. Alternatively, it can be suitably used as a catalyst for various reactions. In particular, those having a large specific surface area and containing nitrogen have a high ability to adsorb not only hydrocarbon solvents such as benzene but also compounds containing heteroatoms such as pyridine or mercaptan. The present invention will be described in more detail below with reference to Examples. 1. Method for measuring 0.1-100μ particles Sample approximately 0.1g of each sample. Such sampling is performed five times from different locations for one sample. One portion of each approximately 0.1 g sample was placed on a microscope slide glass. To facilitate observation of the sample placed on a slide glass, spread it out so that the particles do not overlap as much as possible. Microscopic observation shows that granular or powdery substances and/or their secondary aggregates are observed in the visual field under an optical microscope.
Do this for about 50 locations. It is usually desirable to observe at a magnification of 10 ² to ^{10 3} times. The sizes of all particles present in the field of view under the light microscope are read and recorded by a measurer in the field of view under the light microscope. The content (%) of particles of 0.1 to 100μ is determined by the following formula. Content rate (%) of 0.1 to 100 μ particles = N ₁ /N ₀ × 100 N ₀ : Total number of particles whose dimensions have been read under the microscope field N ₁ : Of particles with dimensions of 0.1 to 100 μ out of N ₀ Number: The content of particles of 0.1 to 100μ is expressed as the average value of the results of five samples for one sample. 2. Amount passing through a 150-meter mesh sieve After massaging the dried sample thoroughly by hand if necessary, accurately weigh out approximately 10 g of it, and shake it through a 150-meter mesh sieve in small portions over 5 minutes (size of sieve). ;200mmφ, shaking conditions;200RPM)
After adding the sample, shake for another 10 minutes. The amount of passage through the 150 Tyler mesh is calculated using the following formula. 150 Amount passing through Tyler mesh (weight %) = ω ₀ - _{ω 1} / ω ₀ × 100 ω ₀ : Input amount (g) ω ₁ : Amount remaining on the sieve without passing through 150 Tyler mesh sieve (g ) 3 Measurement of infrared absorption spectrum and determination of absorption intensity (see Figure 1 of the attached drawings) Regarding the measurement sample prepared by the usual KBr tablet method using an infrared spectrophotometer (Model 225) manufactured by Hitachi, Ltd. Infrared absorption spectra were measured. 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. The transmittance at the top of that peak is
When expressed as tp and the baseline transmittance at that wavelength is expressed as tb, the absorption intensity D at that specific wavelength is given by the following formula. D=logtb/tp Therefore, for example, the ratio of the absorption intensity of the peak between 960 and 1020 cm ^-1 and the absorption intensity of the peak between 1450 and 1500 cm -1 is the ratio of the respective absorption intensities calculated using the above formula (D _{960 to 1020} / D _1450-1500 ). 4 Thermal adhesion measurement method for investigating thermal adhesion at 100℃
Prepare the material inserted between two sheets of 0.2 mm thick stainless steel, and press it with a heat press machine (single-action compression molding machine manufactured by Shinto Metal Industry Co., Ltd.) preheated to 100℃ for 5 minutes to create an initial pressure. Pressed at 50Kg. After releasing the press, the hot-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 fusible properties, and if there is almost no difference between before and after hot pressing, the sample is judged to be It was judged to be infusible. 5. Methanol solubility Accurately weigh approximately 10 g of the sample (the accurately weighed weight is defined as W ₀ ), and dissolve it in approximately 500 ml of substantially anhydrous methanol.
Heat under reflux for 30 minutes. Filter through a glass filter (No. 3), wash the filter residue sample on the filter with about 100 ml of methanol, and then filter the filter residue sample at 40℃ for 5 minutes.
It was dried for an hour (the exact weighed weight is W ₁ ). Methanol solubility (S ₁ %) was determined using the following formula. Methanol solubility (S ₁ % by weight) = W ₀ − W ₁ /W ₀ ×100 6 Determination of free phenol content Approximately 10 g of a sample passed through a 150-meter mesh was accurately weighed, and 30 g of substantially anhydrous methanol was dissolved in 190 g of substantially anhydrous methanol.
Heat under reflux for a minute. The liquid passed through a glass filter (No. 3) was subjected to high-performance liquid chromatography (6000A manufactured by Waters, USA).
The phenol content in the applied solution was determined, 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. Equipment: 6000A manufactured by Waters Co., USA Column carrier: μ-BondapakC ₁₈ Column: 1/4 inch diameter x 1 foot length Column temperature: Room temperature Eluent: Methanol/water (3/7, volume ratio) Flow rate: 0.5 ml/min Detector: UV (254nm), Range0.01 (1
mV) The phenol content in the liquid was determined from a previously prepared calibration curve (relationship between phenol content and peak height based on phenol). 7. Bulk density: It is cut off at the 100ml mark.
Pour the sample that has passed through the 100 ml mesh into a 100 ml graduated cylinder from 2 cm above the rim of the graduated cylinder. The bulk density is determined by the following formula. Bulk density (g/ml) = W (g)/100 (ml) W: Weight per 100 ml (g) 8 Density of carbon molded body A sample was crushed and measured by the float-sink method. 9 Hardness of carbon molded body Measured using a Bitkers microhardness tester at a load of 500 kg. 10 Bending strength of carbon molded body Measured according to JIS-K-6911. 11 Gas permeability of carbon molded body Measured by volume change method using helium gas with an apparatus according to ASTM D-1434. 12 Heat resistance of carbon molded body TG heated at a heating rate of 5℃/min in air
Measurement was performed using A device at the temperature at which weight loss started. 13 X-ray diffraction pattern of carbon compact The sample was crushed with a tungsten carbide disc type crusher, and CuK was crushed using a nickel filter.
It was measured using a diffractometer using alpha rays. 14 Electrical specific resistance of carbon molded body Measured by voltage drop method according to JIS-R-7202. Reference Example 1 (1) Put 1500 g of each mixed aqueous solution at 25°C consisting of various compositions of hydrochloric acid and formaldehyde (listed in Table 1) into 2 separable flasks, and
98% by weight phenol (the remaining 2% by weight is water),
Prepared using urea and 37% by weight formalin and water. 125 g each of a mixed aqueous solution (25° C.) containing 20% by weight phenol, 20% by weight urea and 14.6% by weight formaldehyde was added. After adding and stirring for 15 seconds, it was left to stand for 60 minutes. While standing for 60 minutes, some of the contents in each separable flask remained transparent (Run No. 1 and Table 1).
20), and some changed from transparent to cloudy and remained cloudy (Run No. 3, 9 and 9 in Table 1).
18), and some changed from transparent to cloudy and gave a white precipitate (Run No. 2, 4 to 4 in Table 1).
8, 10-17 and 19). This white precipitate contains
When observed under a microscope, spherical objects, aggregates of spherical objects, and a small amount of powder were already observed. Next, the contents of each separable flask were heated to 80°C for an additional 60 minutes with occasional stirring, and then
Incubate the reaction product at 40-45℃ for 15 minutes at a temperature of 80-82℃
Wash with warm water of 0.5% by weight ammonia and 50%
In a mixed aqueous solution consisting of 60% methanol by weight
℃ for 30 minutes, washed again with warm water at 40-45℃ and dried at 80℃ for 2 hours. Table 2 shows the properties of reaction products obtained from mixed aqueous solutions of hydrochloric acid and formaldehyde of various compositions. (2) On the other hand, the following experiment was conducted for comparison. 1
Distilled phenol in a separable flask.
Add 282g, 369g of 37% by weight formalin, and 150g of 26% by weight aqueous ammonia, raise the temperature from room temperature to 70℃ in 60 minutes while stirring, and then
Stir and heat for 90 minutes at a temperature of 70-72°C. Next, the mixture was allowed to cool, and dehydration was carried out by azeotropic distillation under a reduced pressure of 40 mmHg while adding 300 g of methanol little by little. 700 g of methanol was added as a solvent, and a transparent yellow-brown resol resin solution was taken out. 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 is further heated at a temperature of 160℃ under nitrogen gas.
After heat curing for 60 minutes, the resulting cured foam was crushed to obtain a small amount of powder that passed through a 150 Tyler mesh sieve. In this case, the thermosetting resol resin is extremely hard, and it is extremely difficult to obtain a powder of 150 mesh passes even using various types of crushers, ball mills, or vibrating mills for fluorescent X-rays.
The thus obtained thermosetting resol resin powder was mixed with 0.5% by weight of ammonia under the same conditions as described above.
It was treated with a mixed aqueous solution consisting of 50% by weight methanol, washed with warm water and then dried. The properties of the sample thus obtained are listed in Table 2 as Run No. 21. Next, put 390 g of phenol, 370 g of 37% by weight formalin, 1.5 g of oxalic acid, and 390 g of water into a separable flask, and while stirring.
Raise the temperature to 90℃ in 60 minutes, and at a temperature of 90-92℃
Stir and heat for 60 minutes. Then 35% by weight hydrochloric acid
1.0 g was added, and the mixture was further stirred and heated at a temperature of 90 to 92°C for 60 minutes. Next, 500 g of water was added and cooled, the water was removed by a siphon, and the mixture was heated under a reduced pressure of 30 mmHg and heated at a temperature of 100° C. 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 resulting novolac resin was obtained as a tan solid upon cooling. This one has a softening temperature of 78
~80°C, and the free phenol content determined by liquid chromatography was 0.76% by weight. The above novolac resin was ground and mixed with 15% by weight of hexamethylenetetramine, the mixture was heat cured in nitrogen gas at a temperature of 160°C for 120 minutes, then ground in a ball mill and passed through a sieve of 150 Tyler mesh. I forced it. The powder thus obtained was treated with a mixed aqueous solution of 0.5% by weight ammonia and 50% by weight methanol under the same conditions as described above, washed with warm water and then dried. The properties of the sample thus obtained are listed in Table 2 as Run No. 22. Furthermore, the above novolac resin was made with a hole diameter of 0.25mmφ.
Melt spinning was carried out at a temperature of 136-138°C using a spinneret with 120 holes. Obtained average fineness 21
Denier spun yarn is mixed into an aqueous solution containing 18% by weight of hydrochloric acid and 18% by weight of formaldehyde.
It was immersed for 60 minutes at a temperature of 20-21°C, then raised to a temperature of 97°C over 5 hours, and held at a temperature of 97-98°C for 10 hours. The thus obtained cured novolak fibers were washed with hot water under the same conditions as described above, treated with a mixed aqueous solution consisting of 0.5% by weight ammonia and 50% by weight methanol, washed with warm water, and then dried. This material was ground in a ball mill. The properties of the material that passed through the 150 Tyler mesh sieve are listed in Table 2 as Run No. 23. (3) Table 1 shows the hydrochloric acid and formaldehyde used, the total concentration of hydrochloric acid and formaldehyde, the ratio of the weight of the hydrochloric acid-formaldehyde solution to the total weight of phenol and urea, and the ratio of formaldehyde (mol) to phenol (mol) and urea (mol). mol) and the total molar ratio is shown. Also,
Table 2 shows the results obtained by microscopic observation of the obtained samples.
Content of particles 0.1-50μ and 0.1-100μ,
The amount of passage through the sieve (150 mesh pass) when the obtained sample was passed through a 150-meter mesh sieve and the infrared absorption spectroscopy of the obtained sample
960~1020cm ^-1 , 1280~1360cm ^-1 and 1580~
The absorption wavelength intensity ratio (IR intensity ratio) of the absorption intensity at 1650 cm ^-1 to the absorption intensity between 1450 and 1500 cm ^-1 is shown.

【table】

[Table] Run No. 1, 2, 6, 17 and
In 20 experiments, many sticky resins and hard large lumps or plates were formed at the bottom of the separable flask. Also, in Run Nos. 1, 2, and 20, less than 49 g of solid was obtained from the 25 g of phenol and 25 g of urea used. The content (%) of 0.1-50μ and 0.1-100μ particles and 150 mesh pass (% by weight) listed in Table 2 for Run Nos. 1, 2, 3, 6, 17 and 20 are based on the adhesive resin, The value is for granular or powdery materials relative to the total solids including lumps and plate-like materials. However, the content (%) of 0.1 to 50 μ and 0.1 to 100 μ particles in only granular or powdered solids produced in these experiments and the numerical values of 150 mesh pass (% by weight) are shown in Table 2. It was the value shown when closed with a cutlet. From the above experimental facts including the results listed in Table 2, Run Nos. 1, 2, 3, 6, 17 and 20 cannot be recommended as manufacturing methods. However, even with these manufacturing methods, if we limit ourselves to the granular or powdery products produced, these granular or powdery products are sufficiently suitable for use as the granular or powdery nitrogen-containing resin used in the present invention. It has the following characteristics. FIG. 1 of the accompanying drawings shows an infrared absorption spectrum diagram of the granular or powdery material obtained in Run No. 12. In addition, FIG. 1 also shows the following information, which is required when determining the absorption intensity D from the infrared absorption spectrum diagram.
The method for determining t _p and t _b is illustrated. A baseline is drawn at a certain peak, and t _p and t _b at that wavelength are determined as illustrated. Reference Example 2 10 kg of a mixed aqueous solution consisting of 18% by weight hydrochloric acid and 11% by weight formaldehyde was placed in each of 20 6 reaction vessels in a room at a room temperature of 21 to 22°C. 3.34% of a mixed aqueous solution consisting of 30% by weight of phenol, 20% by weight of urea and 11% by weight of formaldehyde was added to each flask while stirring at a temperature of 23°C.
Kg, 2.66Kg, 1.60Kg, 1.06Kg, 0.74Kg and 0.45
Kg added. The bath ratios in this case are 7.0, 8.5, and
They were 13.5, 20.0, 28.0 and 45.0. In either case, when the mixed aqueous solution was continued to be stirred after being added, it rapidly became cloudy in 10 to 60 seconds. As soon as the mixture became cloudy, stirring was stopped and the mixture was allowed to stand for 3 hours. Thirty minutes after the internal temperature gradually rose and the mixture became cloudy, a white slurry or resin-like substance was observed in each case. The contents of each were then washed with water while stirring. In this case, in the system with a bath ratio of 7.0, a large amount of resin-like cured material fused to the stirring rod, making stirring very difficult. Next, the contents were treated in a 0.3% by weight ammonia aqueous solution at a temperature of 30°C for 2 hours with gentle stirring, washed with water, and then dehydrated. The resulting granular, powdery or lumpy material was lightly kneaded by hand and dried at a temperature of 40° C. for 3 hours. The moisture content after drying is 0.5 in each case.
It was less than % by weight. The contents are Run No. 31, 32, 33, 34, 35 and
36. Table 3 shows the maximum temperature reached in the reaction system from the start of the reaction until 3 hours after it becomes cloudy, the yield of the reaction product, the presence or absence of spherical primary particles as determined by microscopic observation, and the proportion of 150 tyers in the reaction product. The content of the mesh-passed product, the bulk density of the 150-mesh-passed product, the thermal fusibility of the reaction product at 100°C, the methanol solubility, and the free phenol content are shown.

[Table] In Table 3, the free phenol contents of Run No. 21, 22 and 23 (comparative examples shown in Table 1) are values measured for resol resin and novolac resin before heat curing, and are in parentheses. It was shown to. In Table 3, in the experiment of Run No. 31, sticky resin and lumps amounted to about 80% of the total solids formed at the bottom of the flask. Granules or powders accounted for only about 20% of the total solids produced, but about 85% of them passed through a 100 mesh sieve. The presence or absence of spherical primary particles in Run No. 31 is small because the proportion of granular or powdery materials in the solid matter is as small as about 20%. Therefore, although the method of Run No. 31 is not recommended as a manufacturing method, the produced granules or powders have sufficient characteristics of the granules or powders preferably used in the present invention. Furthermore, Run
Almost all of the granular or powdery materials Nos. 31 to 36 had a particle size of 0.1 to 100 μ. Reference Example 3 A mixture of 20% by weight hydrochloric acid and 8% by weight formaldehyde placed in the separable flask from 2 at 24°C.
While stirring 1250 g of a mixed aqueous solution, add a solution of phenols and nitrogen-containing compounds diluted to 20-80% by weight with 37% formalin so that the total amount of phenols and nitrogen-containing compounds is 50 g. Prepared and added to the bath. When the solution was added, it became cloudy,
The color instantly changed to white, pink, or brown, and stirring was stopped 10 seconds after the solution was added. After stopping the stirring, let it stand for 60 minutes, then raise the temperature to 75℃ for 30 minutes while stirring again, and then keep it at a temperature of 73 to 76℃.
Hold for 60 minutes. Each reaction product was washed with water, then treated in a mixed aqueous solution consisting of 0.3% by weight ammonia and 60% by weight methanol at a temperature of 45°C for 60 minutes, washed with water, and then dried at a temperature of 80°C for 3 hours. Table 4 shows the types and proportions of the phenols and nitrogen-containing compounds used, the concentrations of the diluted solutions of the phenols and nitrogen-containing compounds used in formalin,
The color of the reaction product 60 minutes after addition of this diluted solution, the yield of the reaction product based on the total amount of phenols and nitrogen-containing compounds used, and the proportion of the reaction product in the reaction product.
The content of 0.1-50μ particles, the amount of reaction product over 150 mesh passes, and the infrared absorption spectrum intensity ratio are shown.

[Table] Reference example 4 18
1000 g of a mixed aqueous solution containing 9% by weight of hydrochloric acid and 9% by weight of formaldehyde at 18° C. was added. Room temperature is 15
It was warm at ℃. While stirring each of these, first dissolve 15 g of urea, then add 25 g of diluted mixture containing 80% by weight of phenol and 5% by weight of formaldehyde.
g was added to each at once. In both cases, stirring was stopped 10 seconds after the diluent was added and the mixture became stationary, but 18 to 19 seconds after the stirring was stopped, the mixture suddenly became cloudy and a milky white product was observed. The temperature of each liquid gradually rose from 18℃ and reached 31-32 within 5-7 minutes after adding the diluent.
It reached a peak in °C and then fell again. After adding the diluted solution, run for 0.5 hours (Run No. 61), 1 hour (Run No. 61),
No. 62), 3 hours (Run No. 63), 6 hours (Run
No. 64), 24 hours (Run No. 65), 72 hours (Run
No.66) After leaving it at room temperature, wash the contents with water and 0.75
After treatment in wt.
Dry for an hour. Table 5 shows the passing rate of the obtained dry sample through a 150-meter mesh sieve, the IR intensity ratio of 960 to 1020 cm ^-1 ,
The amount of methanol dissolved and the free phenol content are shown. In addition, all of the samples of Run No. 61 to Run No. 66 were fused in a heat fusion test at 100° C. for 5 minutes.

[Table] Reference Example 5 800 kg of a mixed aqueous solution at 22.5°C consisting of 18.5% by weight hydrochloric acid and 8.5% by weight formaldehyde was placed in a 1000°C reaction vessel equipped with a stirring rod, and the mixed aqueous solution was heated at 20°C while stirring. wt% phenol and 10
40 kg of a mixed aqueous solution consisting of hydroquinone (wt%) and urea (20wt%) was charged. After adding the entire amount of the mixed aqueous solution and stirring for 20 seconds, stirring was stopped and the mixture was left standing for 2 hours. In the reaction vessel, rapid cloudiness was observed 35 seconds after the entire amount of the mixed aqueous solution was added, white granules were gradually formed, and the internal temperature gradually rose to 35.5°C and then dropped again. Next, while stirring the mixed aqueous solution system of the reaction product again, open the valve attached to the bottom of the reaction vessel to take out the contents, and use a Nomex nonwoven fabric to remove the reaction product, the hydrochloric acid, and formaldehyde. The mixed aqueous solution was separated.
The reaction product thus obtained was washed with water, dehydrated, and then heated to 18°C.
After being immersed in a 0.5% by weight ammonia aqueous solution for a day and night, the product was washed again with water and dehydrated to obtain 29.9 kg of a reaction product with a water content of 15% by weight. 2.0Kg of the reaction product obtained by the above method was dried at a temperature of 40℃ for 3 hours to obtain 1.7Kg of sample (Run
No.67). Table 6 shows the content of 0.1-50μ and 0.1-100μ particles as determined by microscopic observation of the dried sample thus obtained;
The amount passed through a 150-meter mesh sieve (150 mesh pass) and methanol solubility are shown.

[Table] Example 1 100g of Run No. 12 product (as filler)
and resol resin used in Run No. 21 (uncured material,
(100g in terms of solid content) were mixed. The resulting resin mixture was dried at room temperature overnight and then at 80°C.
Dry for 30 minutes in an open dryer. A certain amount of the obtained material was processed for 30 minutes under a pressure of 200Kg/cm ² using a mold preheated to 150℃, and the dimensions were
Five molded products of 20 mm, thickness 3 mm, and length 120 mm were made. Similarly, as a filler, the product of Run No. 40, the product of Run No. 47, the product of Run No. 50,
Using the product (cured product) obtained in Run No. 22, wood flour, carbon black, and silica powder each passed through a 100-meter mesh sieve, equal amounts of each were mixed with the resol resin used in Run No. 21. Five molded products (precursors) each having dimensions of 20 mm in width, approximately 3 mm in thickness, and 120 mm in length were made from various fillers and resol resin in the same manner as described above. Next, these precursors were heated at a rate of 30°C/hour from room temperature to 1000°C under nitrogen gas flow,
It was further held at a temperature of 1000°C for 60 minutes. after that,
It was slowly cooled to obtain a carbonized fired product (carbon compact). Table 7 shows the type of filler used, length retention rate (relative to the precursor), carbonization yield (relative to the precursor), Vickers hardness, gas permeability, and bending strength of the carbonized fired product. Ta.

[Table] In Table 7, the carbonized and fired products of Run No. 75 and Run No. 76 were both bent and broken due to cracks and/or gas blisters, and the length retention rate was low. Measurement was difficult. Furthermore, there is a large variation in hardness. Example 2 Run No. 65 product (as filler) and Run
The resol resin (uncured product) used in No. 21 was mixed in various proportions (referred to as Run No. 79 to Run No. 86), air-dried at room temperature for 24 hours, and then heated to 60°C for 60 hours. Dry for a minute. Approximately 50 g of each sample was divided into 10 equal parts and processed under a pressure of 300 kg/cm ² for 20 minutes using a mold preheated to 150°C in a hot press machine, and the dimensions were 13 mm wide. Thickness 3.2~3.4mm, length 100mm
Ten molded products were obtained for each sample. Next, these molded products (precursors for carbonization firing) were heated from room temperature to 100°C in 30 minutes under nitrogen gas flow, held at 100°C for 30 minutes, and then heated again.
It took 50 hours to reach the temperature of 1500℃, then the temperature reached 1500℃.
℃ temperature 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 8 shows the mixing ratio of the product of Run No. 65 and the resol resin (in terms of solid content) in the experiments of Run No. 79 to Run No. 86, the appearance and specific gravity of the precursor, and the results of each of the 10 carbonized and fired products. The number of specimens with no noticeable cracks or gas blisters (non-defective products), specific gravity, carbonization yield, bending strength, and electrical resistivity measured using non-defective products are shown. In addition, since we were unable to obtain a good product for Run No. 79,
Only specific gravity and carbonization yield are shown. In addition, a glass-like luster was observed on the fracture surface of all carbonized and fired products, and the X-ray diffraction pattern showed 22
It had a broad peak around ~24°.

[Table] Example 3 Precursor sample consisting of 40 parts by weight of the product of Run No. 41 (as filler) and 60 parts by weight of the resol resin (uncured product, solid content equivalent) used in Run No. 21
40 pieces were made in the same manner as in Example 2. Five samples each were heated from room temperature to 40°C under helium gas flow.
350℃ (Run No.87), 450℃ at a rate of ℃/hour
(Run No.88), 550℃ (Run No.89), 650℃
(Run No.90), 800℃ (Run No.91), 1000℃
(Run No.92), 1500℃ (Run No.93), 1800℃
(Run No. 94) or 2100° C. (Run No. 95), held at each temperature (carbonization temperature) for 3 hours, and then allowed to cool. Table 9 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.

[Table] Example 4 50 parts by weight of the product of Run No. 13 (as a filler), the resol resin (uncured product) used in Run No. 21, and the novolak resin obtained in Run No. 22 (hexamethylenetetramine). 10% by weight), Run
Product of No. 63 (thermal adhesive product), Product of Run No. 67 (thermal adhesive product), Furan resin (Hythafuran)
303; manufactured by Hitachi Chemical Co., Ltd.), epoxy resin (Epicoat
815; Ciel Chemical Co., Ltd.) or coal tar pitch (softening point 125°C, quinoline insoluble matter 13.6%; Allied Chemical Co., Ltd.) according to the method of Example 2, using 50 parts by weight each in terms of solid content. and mixed to obtain mixtures of various compositions. Next, 2.5g of mixtures of various compositions per sample.
The molded products were molded according to Example 2 to obtain 10 molded products (precursors) each having dimensions of 13 mm in width, 1.5 to 1.7 mm in thickness, and 100 mm in length. The precursor obtained by the above method was heated gradually from room temperature to 1000°C over 24 hours while flowing nitrogen gas, maintained at 1000°C for 60 minutes, and then allowed to cool. Table 10 shows the type of resin used, the number of samples (good products) with no cracks or gas blisters among the 10 samples obtained by carbonization firing, and the carbonization yield and bending strength of the good products. .

[Table] Example 5 Product of No. 50, coconut shell powder of 100 tyler mesh pulverized after heat treatment at a temperature of 500°C under nitrogen atmosphere, wheat flour of 100 tyler mesh, polyvinyl of 100 tyler mesh 40 parts by weight each of alcohol or 100% silica powder and 60% of the product of Run No. 35.
5 types of mixtures consisting of parts by weight (Run No.103
~ Run No. 107) or the product of Run No. 35 (Run No. 108) alone in a small extruder (manufactured by Sumitomo Heavy Industries, Ltd., type: 3AGM) at 150°C.
A rope with a diameter of 2 to 3 mm was extruded at a temperature of . Thereafter, the pieces were cooled with water and cut into lengths of about 10 mm, and dried at a temperature of 80° C. for 5 hours to obtain a precursor for carbonization and firing. Next, the temperature of the above precursor was raised from room temperature to 900°C in 60 minutes while continuing to feed nitrogen containing water vapor passed through hot water at 80°C, and then heated to 900°C.
After being kept at a temperature of 30°C for 30 minutes, it was cooled and taken out. Table 11 shows 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 and equilibrium adsorption amount of benzene at 20°C by the BET method ( _N2 method) are shown.

[Table] Example 6 The uncured novolak resin (containing 10% by weight hexamethylenetetramine) used in Run No. 22 was
65 parts by weight used as a matrix, and as a filler the product of Run No. 12, the product of Run No. 64,
A powder mixture of 35 parts by weight of each of Run No. 21 powder (cured product), Run No. 22 powder (cured product), and Run No. 23 powder (cured product) was prepared in advance.
It was put into a melter heated to 160℃ and extruded through a nozzle with a diameter of 1mm under a pressure of 5Kg/cm ² to obtain a material with dimensions of 50℃.
It was received in a mm square mold with a depth of 10 mm. Each of the plate-shaped products thus obtained was cooled to room temperature, heat-treated in a dryer heated to 80°C for 8 hours, and further heated at 120°C for 4 hours, then removed from the mold and crushed. The material passed through the mesh sieve was used as a precursor. Next, the precursor obtained by the above method was placed in an electric furnace, and the temperature inside the furnace was raised from room temperature to 850°C while continuing to feed steam-containing nitrogen passed through hot water at 85°C.
The temperature was raised to 850°C in 90 minutes, and the temperature was further maintained at 850°C for 60 minutes. Table 12 shows the type of filler used, the extrudability of the mixed powder from the nozzle, the nitrogen content determined by elemental analysis of the carbonized and fired product, the specific surface area determined by the BET method ( _N2 method), and the adsorption amount of ethyl mercaptan. Ta.

【table】 [Brief explanation of the drawing]

FIG. 1 of the accompanying drawings is an infrared absorption spectrum diagram of an example of a granular or powdery nitrogen-containing phenol formaldehyde resin used in the present invention. FIG. 1 also illustrates a method for determining the absorption intensity at a specific wavelength of the peak.

Claims (1)

[Scope of Claims] 1. A granular or powdery resin comprising a phenol, a nitrogen-containing compound having at least two active hydrogens, and a condensate with an aldehyde, wherein (A) the granular or powdered resin is a granular or powdery resin; Contains spherical primary particles with a diameter of 0.1 to 100 microns and secondary aggregates thereof, and (B) In the infrared absorption spectrum of the resin by the KBr tablet method, the largest absorption intensity in the range of 1450 to 1500 cm ^-1 is D _{1450 ~1500} , and the largest absorption intensity in the range of 960 to 1020 cm ^-1 is expressed as D _{960 to 1020} , where D _{960 to 1020} / D _{1450 to 1500} = 0.1 to 2.0. A precursor molded body is thermoformed from a thermoformable resin composition containing at least a nitrogen phenol aldehyde resin, or a thermoformable version of the granular or powdered nitrogen-containing phenol aldehyde resin, and then a precursor molded body is formed. A method for producing a carbon molded body, characterized by carbonizing and firing. 2 At least 30% of the granular or powdered nitrogen-containing resin
% of spherical primary particles with a particle size of 0.1 to 100 microns and secondary aggregates thereof. 3 The granular or powdered nitrogen-containing resin has the largest absorption intensity in the range of 1280 to 1360 cm ^-1 (absorption peak attributed to carbon-nitrogen bonds) in the infrared absorption spectrum measured by the KBr tablet method.
The method according to claim 1 or 2, wherein when expressed as _D1280-1360 , _D1280-1360 / _D1450-1500 =0.15-3.0. 4. The granular or powdered nitrogen-containing resin is described in any one of claims 1 to 3, wherein _D960-1020 / _D1450-1500 is 0.15-0.6 in an infrared absorption spectrum measured by the KBr tablet method. method. 5. The granular or powdered nitrogen-containing resin has a D _1280-1360 /D _1450-1500 of 0.2-2.0 in an infrared absorption spectrum determined by the KBr tablet method. Method. 6. The method according to any one of claims 1 to 5, wherein the granular or powdered nitrogen-containing resin has a D _{1280 to 1360} /D _{1450 to 1500} of 0.3 to 1.5 in an infrared absorption spectrum measured by the KBr tablet method. . 7. The method according to any one of claims 1 to 6, wherein the granular or powdered nitrogen-containing resin has a size such that at least 50% by weight of the entire nitrogen-containing resin can pass through a sieve of 150 Tyler mesh. 8. Claim 1, wherein the granular or powdered nitrogen-containing resin has a free phenol content of 500 ppm or less as measured by liquid chromatography.
7. The method according to any one of items 7 to 7. 9 The granular or powdered nitrogen-containing resin contains at least 1% by weight of nitrogen.
The method described in any of the paragraphs. 10 The granular or powdered nitrogen-containing resin contains 2 nitrogen
10. The method according to any one of claims 1 to 9, containing ~30% by weight. 11 The granular or powdered nitrogen-containing resin is one in which at least a portion of the resin is fused when the resin passed through a 150 tyler mesh is held at a temperature of 100°C for 5 minutes at an initial pressure of 50 kg. Range 1st to 10th
The method described in any of the paragraphs. 12 When 10 g of the granular or powdery nitrogen-containing resin is heated under reflux in 500 ml of substantially anhydrous methanol, the following formula S=W ₀ −W ₁ /W ₀ ×100 is obtained, where W ₀ is used. The weight of the resin (g), W ₁ is the weight (g) of the resin remaining after heating and refluxing, S indicates the methanol solubility (wt%) of the resin, and the methanol solubility is 20 wt% or more. A method according to any one of claims 1 to 11. 13. The granular or powdery nitrogen-containing resin does not substantially melt or fuse when the resin passed through a 150 tyler mesh is held at a temperature of 100°C for 5 minutes at an initial pressure of 50 kg. 10. The method according to any one of Item 10. 14 The thermoformable granular or powdered nitrogen-containing resin consists of a resin that is at least partially fused when the resin passed through a 150 tyler mesh is held at a temperature of 100°C for 5 minutes. or a material that does not substantially melt or fuse under the same conditions. 15 When the resin passed through the 150 tyler mesh is held at a temperature of 100°C for 5 minutes, at least a portion of it will fuse and a portion that will not substantially melt or fuse, and at least a portion of the above 15. The method of claim 14, wherein at least 10% by weight of the fused material is fused. 16. The method according to claim 1, wherein the thermoformable resin composition further contains another carbonized material in addition to the granular or powdery nitrogen-containing resin. 17. The method of claim 16, wherein the carbonized material is a first carbonized material that is a curable resin. 18. The method of claim 17, wherein the first carbonized material is a thermosetting resin. 19. The method according to claim 18, wherein the thermosetting resin is a resol resin, a novolak resin, an epoxy resin, a furan resin, a melamine resin or a urea resin. 20. The method according to claim 16, 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. 21. The method according to claim 16, wherein the carbonized material is a second carbonized material selected from carbohydrates, derivatives of carbohydrates, or natural products containing carbohydrates as a main component. 22. The method of claim 21, wherein the carbohydrate is cellulose, starch or sugar. 23. The method according to claim 16, wherein the carbonized material is a third carbonized material selected from thermoplastic resins and thermoinfusible resins other than cured products of curable resins. 24. The method according to claim 23, wherein the thermoplastic resin is polyamide, polyvinyl acetate, vinyl chloride, vinylidene chloride or polyacrylonitrile resin. 25. The method according to claim 23, wherein the heat-infusible resin is polyvinyl alcohol or polyvinyl formal. 26 Claim 1 or 1, wherein the thermoformable resin composition further contains an inorganic filler
The method described in Section 6. 27. The method of claim 26, wherein the inorganic filler is silica, alumina, silica-alumina, calcium carbonate, calcium silicate, or a noble metal. 28 The thermoformable resin composition comprises (a) a granular or powdered phenol aldehyde nitrogen-containing resin, (b) a curable resin (first carbonized material), and/or (c) the second or 3, the granular or powdered nitrogen-containing resin of (a) above accounts for at least 10% by weight of the total composition, and the granular or powdered nitrogen-containing resin of (a) above. 2. A method according to claim 1, wherein the thermoformable material and/or the second carbonized material of (b), individually or in combination, is at least 20% by weight of the total composition. 29 The granular or powdered nitrogen-containing resin of (a) above is at least 20% by weight of the total composition, and the granular or powdered nitrogen-containing resin of (a) above is thermoformable and/or 29. The method of claim 28, wherein the amount of the second carbonized materials of b), alone or in total, is at least 30% by weight of the total composition. 30 The granular or powdered nitrogen-containing resin in (a) above is at least 30% by weight of the total composition, and the granular or powdered nitrogen-containing resin in (a) above is thermoformable and/or the nitrogen-containing resin in the above (a) is 30. The method of claim 29, wherein the amount of the second carbonized materials of b), alone or in total, is at least 40% by weight of the total composition. 31. The method according to any one of claims 1 to 30, wherein the carbonization calcination is carried out at a temperature of about 450°C or higher. 32. The method of claim 31, wherein said carbonizing calcination is carried out at a temperature between about 500 and about 2500<0>C. 33. The method according to any one of claims 1 to 32, wherein the carbonization firing is performed in a non-oxidizing atmosphere. 34. The method of claim 33, wherein the non-oxidizing atmosphere is substantially free of molecular oxygen. 35. The method according to claim 33 or 34, wherein the non-oxidizing atmosphere contains at least one selected from nitrogen, helium, hydrogen, and carbon monoxide as a main atmospheric gas. 36 Claims 1 to 32, wherein the carbonization firing is carried out in an atmosphere containing water vapor or carbon dioxide.
The method described in any of the paragraphs.