JP2008169269A - Higher order aggregate particles of phenolic resin fine spheres, method for producing the same, higher order aggregate particles of carbon fine spheres - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide higher order aggregate particles of phenolic resin fine spheres, which have an extremely small metal impurity content and not needing a grinding process. <P>SOLUTION: The higher order aggregate particles of phenolic resin fine spheres are characterized in that the phenolic resin fine spheres form three-dimensional structures. The phenolic resin fine spheres have an average small diameter of 0.1 to 10 micron meter, and the higher order aggregate particles have an average radius of 0.1 to 1,000 micron meter. The higher order aggregate particles are produced by polymerizing a phenol compound with an aldehyde compound in the presence of an ammonium salt such as ammonium carbonate, ammonium bicarbonate or ammonium acetate. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to high-order aggregate particles of phenol resin microspheres, a method for producing the same, and high-order aggregate particles of carbon microspheres.

  The aggregates of organic polymer microspheres are usually obtained by a sol-gel method in which phenols and aldehydes are polymerized in an aqueous medium, and are called organic polymer gels. This organic polymer gel forms a higher-order structure by colloidal fine particles of resol type phenolic resin being three-dimensionally aggregated or cross-linked. Usually, the particle diameter of the primary particles constituting the organic polymer gel is in the range of 10 nm to 100 nm corresponding to the size of the colloidal fine particles, and when the primary particles are aggregated or crosslinked, the entire reaction solution is insoluble and infusible mass. It becomes a gel. Carbide produced by carbonizing organic polymer gel is commonly called carbon gel, and has a porous structure with a large pore area and pore volume, so it is used for water and sewage treatment and exhaust gas treatment. Applications as materials, electrode materials, catalysts, etc. are expected, and various studies have been conducted.

  For example, Japanese Patent Laid-Open No. 9-202610 (Patent Document 1) discloses R.A. W. In accordance with the method of Pekala, a method of obtaining a carbon gel by baking an organic polymer gel produced by sol-gel polymerization of resorcinol and formaldehyde in the presence of a catalyst such as sodium carbonate is disclosed.

  However, the organic polymer gel used as the raw material for the carbon gel has many problems. The first problem is that the sol-gel polymerization reaction requires a long time of about 3 to 10 days. Conventionally, an organic polymer gel has been polymerized at room temperature and aged for about 3 to 10 days at a temperature of about 75 to 90 ° C., thereby increasing the strength of the polymer gel. If the process for obtaining the aged organic polymer gel is incomplete, the strength of the polymer gel is insufficient, and the shape cannot be maintained when the carbon gel is generated. Therefore, in the conventional method, the aging process requiring a long time is a serious problem in terms of mass productivity.

  In order to solve the above problems, a method for producing an aged organic polymer gel in a short time has been studied. For example, JP 2002-003211 A (Patent Document 2) discloses polyhydric phenols and formaldehyde. A method for producing a carbon material in which an organic polymer gel is obtained by reacting in water to obtain an organic polymer gel, then water is added, and heat treatment is performed under pressure and sealing to produce an aged organic polymer gel, which is carbonized Is disclosed. However, in the manufacturing method, since a pressure sealed container is used when aging the organic polymer gel, the manufacturing equipment becomes large in terms of the apparatus, and the problem of mass productivity still remains.

  The second problem is that the organic polymer gel is obtained as a lump. Adsorption materials, electrode materials, catalysts, etc., which are useful uses of carbon gels obtained by carbonizing organic polymer gels, are often processed and molded using carbon gel powder, so carbon gel can also be obtained in powder form Is desirable. However, in order to obtain a powdered carbon gel using the organic polymer gel obtained from the lump, the lump organic polymer gel has to be crushed, which increases the manufacturing cost, and during the pulverization process There were problems such as contamination of impurities. On the other hand, Japanese Patent Application Laid-Open No. 2004-315283 (Patent Document 3) reports a method of forming organic polymer gel into fine particles without crushing. In the method, in order to obtain a particulate organic polymer gel, the reaction product obtained by sol-gel polymerization reaction of phenols and aldehydes is emulsion-gelled in the presence of a surfactant to form particles. An organic polymer gel is obtained. In the above method, the viscosity of the reaction product greatly affects the average particle size of the particulate organic polymer gel. However, since the change in the viscosity of the reaction product over time is large, the average particle size of the organic polymer gel can be controlled. difficult. Further, since a surfactant is used, it is difficult to obtain a particulate organic polymer gel at a low cost, such as generation of a large amount of waste solvent. Furthermore, since the shape of the particulate organic polymer gel becomes a true spherical particle due to the properties of the particle formation treatment, there is a problem that the packing density is lowered depending on the application.

The third problem is about the content of metal impurities in the organic polymer gel. When a carbon gel obtained by carbonizing an organic polymer gel is used as an adsorbing material, an electrode material, a catalyst, or the like, it is desirable that the carbon gel has high purity, that is, the content of metal impurities is small. However, since an alkali metal salt is used as a catalyst in the conventional sol-gel polymerization reaction, metal impurities remain in the organic polymer gel, and the content of metal impurities in the carbon gel obtained by using it remains large. There was a problem that it was inferior in purity. By cleaning the carbon gel, the content of metal impurities can be reduced to some extent, but it is difficult to completely remove it, which also affects the cost.
JP-A-9-202610 JP 2002-003211 A JP 2004-315283 A

  An object of the present invention is to provide high-order aggregate particles of phenol resin microspheres that have a very low content of metal impurities and do not require a pulverization step.

  As a result of intensive studies, the present inventors have found that by reacting phenols and aldehydes in an aqueous medium in the presence of an ammonium salt, the high content of phenol resin microspheres having a very low metal content and a unique structure. The present inventors have found that the next aggregate particles can be produced easily and at low cost, and the present invention has been completed based on this finding.

  The present invention relates to (1) higher-order aggregate particles of phenol resin microspheres, wherein the phenol resin microspheres have a three-dimensional structure.

  Further, the present invention provides (2) an average value of R2 / R1, where R2 / R1 is a ratio of the longest diameter R1 of the higher-order aggregate particles to the shortest diameter R2 passing through the midpoint of the longest diameter R1. R (ave) is 0.95 or less, The high-order aggregate particle of the phenol resin microsphere according to the above (1).

  In the present invention, (3) the phenol resin microsphere may have an average diameter of 0.1 to 10 μm, and the phenol resin microsphere may have a high height as described in (1) or (2). It relates to the next aggregate particle.

  Moreover, this invention is (4) The phenol resin of any one of said (1)-(3) characterized by the average particle diameter of the said higher order aggregate particle being 0.1-1000 micrometers. The present invention relates to high-order aggregate particles of microspheres.

  Moreover, this invention is (5) High-order aggregate particle | grains of the phenol resin microsphere of any one of said (1)-(4) characterized by the ash content being 1 weight% or less About.

  The present invention also relates to (6) a method for producing high-order aggregate particles of phenol resin microspheres, wherein a phenol and an aldehyde are polymerized in an aqueous medium in the presence of an ammonium salt.

  The present invention also provides (7) high-order aggregate particles of phenol resin microspheres described in (1) to (5) above or high-order aggregate particles of phenol resin microspheres obtained by the production method described in (6) above. The present invention relates to high-order aggregate particles of carbon microspheres obtained by firing at 500 to 3000 ° C.

  The present invention also relates to (8) the high-order aggregate particles of carbon microspheres according to (7) above, wherein the high-order aggregate particles have an average particle size of 0.1 to 1000 μm.

  In addition, the present invention provides (9) high-order aggregation of carbon microspheres according to (7) or (8), wherein the average microsphere diameter of the carbon microspheres is in the range of 0.1 to 10 μm. It relates to aggregated particles.

  The present invention also relates to (10) the high-order aggregate particles of carbon microspheres according to any one of (7) to (9), wherein the ash content is 2% by weight or less. .

  According to the present invention, high-order aggregate particles of phenol resin microspheres having a very small content of metal impurities, developed pores, and having a porous structure can be easily obtained at low cost.

  The higher-order aggregate particles of the phenol resin microspheres of the present invention are obtained by forming a three-dimensional structure of phenol resin microspheres. Here, the phenolic resin microspheres are colloidal particles of a phenolic resin formed at the initial stage of polymerization (approximately within 10 minutes from the start of polymerization) when a phenol and an aldehyde are polymerized in an aqueous medium in the presence of an ammonium salt. There are minute spherical particles that finally become constituents of the higher-order aggregate particles obtained by the polymerization reaction.

The phenolic resin microsphere high-order aggregate particles of the present invention have a three-dimensional structure in which the phenolic resin microspheres are aggregated by chemical interaction such as cross-linking and covalent bonding or physical interaction such as aggregation. Forming a structure. The form of the assembly of phenol resin microspheres is not particularly limited, but is usually assembled randomly. The high-order aggregate particles of the phenol resin microspheres in the present invention are treated as one particle in order to maintain their shape unless treated by mechanical stress such as pulverization or crushing. Can do. In this way, higher order aggregate particles of phenol resin microspheres that can be handled as a single particle by gathering a plurality of phenol resin microspheres and forming a three-dimensional structure, compared with a cured phenol resin with the same particle size It is excellent in that the external surface area becomes large and can be used for various purposes.
When the ratio of the longest diameter R1 of the high-order aggregate particles of the phenol resin microspheres of the present invention to the shortest diameter R2 passing through the midpoint of the longest diameter R1 is R2 / R1, the average value of R2 / R1 R (ave) is preferably 0.95 or less, more preferably 0.1 to 0.95, and particularly preferably 0.3 to 0.9. When R (ave) exceeds 0.95, the packing density of the higher-order aggregate particles tends to decrease. As the value of R (ave) approaches 1, the shape of the higher-order aggregate particles becomes more spherical, and conversely, the smaller the value, the more fibrous or flat.

  Here, the R (ave) value can be obtained by the following method. First, high-order aggregate particles of phenol resin microspheres are extracted at random, and a projection photograph of the whole particle is taken with an electron microscope. The length of the longest diameter R1 of the projected photograph particles and the shortest diameter R2 passing through the midpoint of the longest diameter R1 are measured, and the ratio R2 / R1 is calculated. This R2 / R1 is defined as an R value, and an R (ave) value can be obtained by calculating an average value for 100 higher-order aggregate particles.

  The average microsphere diameter of the phenol resin microspheres constituting the high-order aggregate of the phenol resin microspheres of the present invention is in the range of 0.1 to 10 μm in that the specific surface area of the high-order aggregate particles can be increased. Preferably, it is in the range of 0.2 to 8.0 μm, more preferably in the range of 0.4 to 6.0 μm. When the average microsphere diameter of the phenol resin microspheres is less than 0.1 μm, higher order aggregates are not obtained as particles, and the whole solution tends to be agglomerated. When the average microsphere diameter exceeds 10 μm, higher order aggregate particles May become excessively large and pulverization may be necessary depending on the application.

  The average microsphere diameter of the phenol resin microsphere can be calculated, for example, from the projection photograph of an electron microscope by the following method. First, high-order aggregate particles of phenol resin microspheres are extracted at random, and a projection photograph of the whole particle is taken with an electron microscope. The longest straight line connecting the two ends of the phenolic resin microspheres constituting the higher-order aggregate of the projected photograph is regarded as the diameter, and the diameters of all the phenolic resin microspheres appearing in the projected photograph are measured. The average value is calculated as the average microsphere diameter of the phenol resin microspheres.

  The average particle diameter of the higher-order aggregate particles of the phenol resin microspheres of the present invention is preferably in the range of 0.1 to 1000 μm, more preferably in the range of 0.5 to 500 μm, in terms of handleability. The range of 1 to 100 μm is particularly preferable. When the average particle size of the high-order aggregate particles is less than 0.1 μm, the particles are likely to scatter and the handling property tends to be poor. When the average particle size exceeds 1000 μm, pulverization may be necessary depending on the application. is there. The average particle size of the higher-order aggregate particles can be calculated as, for example, 50% D of the particle size distribution measured by a laser light scattering particle size distribution measuring device.

  The ash content of the high-order aggregate particles of the present invention is preferably 1% by weight or less, more preferably 0.5% by weight or less, and particularly preferably 0% by weight in terms of purity. preferable. When the ash content exceeds 1% by weight, impurities may be eluted depending on the application, and the properties tend to be adversely affected. The ash content of the higher-order aggregate particles was calculated as a ratio (% by weight) to the total weight of the sample before heating and ashing after measuring the residue weight after heating and ashing the sample in an air atmosphere. It is.

  The method for producing the higher-order aggregate particles of the phenol resin microspheres of the present invention is not particularly limited, and examples thereof include a method in which a phenol and an aldehyde are polymerized in an aqueous medium in the presence of an ammonium salt.

  The amount of phenols and aldehydes used is not particularly limited and is appropriately selected. The molar ratio of aldehydes (aldehydes / phenols) to phenols is preferably 0.8 to 3.0. More preferably, it is 0.0-2.5. When the molar ratio is less than 0.8, the three-dimensional structure is not sufficiently formed, and the specific structure of the higher-order aggregate particles of the phenol resin microspheres of the present invention tends to be hardly expressed. When the molar ratio exceeds 3.0, a large amount of unreacted aldehydes tend to remain.

  Although the usage-amount of an aqueous medium is also selected suitably, it is preferable that it is 1-60 weight part with respect to 1 weight part of total weights of phenols and aldehydes, and it is more preferable that it is 1.5-30 weight part. preferable. By setting the amount of aqueous medium used within the above range, phenols and aldehydes in the reaction solution can be adjusted to an appropriate concentration, and high-order aggregate particles of phenol resin microspheres with uniform composition are generated. It becomes easy to do. When the usage-amount of an aqueous medium is less than 10 weight part, there exists a tendency for the high-order aggregate particle | grains of the phenol resin microsphere with a uniform composition to become difficult to produce | generate. When the amount used exceeds 60 parts by weight, the concentration of phenols and aldehydes tends to be low and the progress of the polymerization reaction tends to be slow, and the structure of the high-order aggregate particles of the resulting phenol resin microspheres There is a tendency to become unstable. In addition, when using the thing of the form of aqueous solution as phenols or aldehydes, the water | moisture content contained in this can also be used as an aqueous medium.

  Examples of the phenolic compound used in the present invention include phenol; resorcinols such as resorcinol; cresols such as o-cresol, m-cresol, and p-cresol; 2,3-xylenol, 2,4-xylenol, 2 Xylenols such as 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol; ethylphenols such as o-ethylphenol, m-ethylphenol and p-ethylphenol; isopropylphenol Propylphenols; butylphenols such as butylphenol and p-tert-butylphenol; p-tert-amylphenol, p-octylphenol, p-nonylphenol, p-cumylphenol, and the like. Not. Among these, in terms of reactivity, those having two phenolic hydroxyl groups per molecule or those having an electron donating substituent at the meta position are preferred, and resorcinol or m-cresol is particularly preferred. These phenols are used alone or in combination of two or more.

  Examples of aldehydes include, but are not limited to, formaldehyde, acetaldehyde, butyraldehyde, salicylaldehyde, benzaldehyde, and the like. Among these, formaldehyde is preferable in that it is water-soluble and has good reactivity with phenols so that the reaction can be performed efficiently and the raw material cost can be reduced. These aldehydes are used alone or in combination of two or more.

  Examples of the aqueous solvent include distilled water, ion exchange water, soft water, and the like, but are not particularly limited thereto. Among these, distilled water or ion-exchanged water is preferable in that the metal ion concentration is low, so that the metal impurity concentration of the resulting high-order aggregate particles of the phenol resin microspheres is reduced and the ash content is reduced.

  In the present invention, it is important to carry out the polymerization reaction in the presence of an ammonium salt, whereby a high-order aggregate having a specific structure can be produced in a short time, and a surfactant is not used. However, it can be recovered as a powder. In contrast, when a basic catalyst other than an ammonium salt, such as an alkali metal salt such as sodium carbonate, is used, the polymerization reaction takes a long time, and metal impurities remain in the product, resulting in poor purity. It ends up. As the ammonium salt, an inorganic ammonium salt or an organic ammonium salt is used. For example, an inorganic ammonium salt such as ammonium carbonate, ammonium hydroxide, ammonium hydrogen carbonate, ammonium sulfate, ammonium hydrogen sulfate, ammonium borate, ammonium nitrate; ammonium acetate, ammonium alginate And organic ammonium salts such as ammonium benzoate, ammonium formate, and ammonium salicylate, and the like are not particularly limited thereto. Among these, ammonium carbonate, ammonium hydrogen carbonate, ammonium acetate, and the like are preferable because they are inexpensive. These ammonium salts are used alone or in combination of two or more. The amount of the ammonium salt used can be appropriately selected in consideration of properties such as the reactivity of phenols or aldehydes and the solubility of the ammonium salt, but is preferably 0.00 per mol of phenols. It is 001-5 mol, More preferably, it is 0.002-3 mol. When the amount of ammonium salt used is within the above range, colloidal particles of phenol resin produced by the polymerization reaction, that is, many phenol resin microspheres are formed in a short time, and therefore higher order aggregate particles of phenol resin microspheres. Can be easily synthesized. When the amount of ammonium salt used is less than 0.001 mol, depending on the amount of aqueous solution used, the concentration of ammonium salt will be low, resulting in insufficient formation of phenol resin colloidal particles, and the polymer resin phase and water. There is a tendency to separate into phases. When the amount of the ammonium salt used exceeds 5 moles, there is no problem with the catalytic action of the ammonium salt, but there is a tendency to be uneconomical because the amount of ammonium salt not involved in the polymerization reaction increases.

  Although the temperature of a polymerization reaction is not specifically limited, Preferably it is 0-100 degreeC, More preferably, it is 10-90 degreeC. When temperature is less than 0 degreeC, there exists a tendency for reaction not to advance easily. When the temperature exceeds 100 ° C., evaporation of the aqueous medium is promoted, so that high-order aggregate particles of phenol resin microspheres tend not to be generated.

  Although the time of a polymerization reaction is not specifically limited, Preferably it is 0.1 to 20 hours, More preferably, it is 0.5 to 10 hours. When the reaction time is less than 0.1 hour, the progress of the polymerization reaction is insufficient, and the structure of the higher-order aggregate particles of the phenol resin microspheres tends to be unstable. When the reaction time exceeds 20 hours, the production time tends to decrease because the reaction time is too long as in the normal sol-gel reaction.

  Higher-order aggregate particles of phenol resin microspheres obtained by the production method of the present invention are obtained from the reaction system through a solid-liquid separation step. The solid-liquid separation method is not particularly limited, and examples thereof include filtration, centrifugation, and spray drying.

  Further, the higher-order aggregate particles of the phenol resin microspheres obtained by solid-liquid separation may be dried as desired, and the drying is performed on the phenol resin microspheres constituting the higher-order aggregate particles of the phenol resin microspheres. Preferably, the liquid content in the three-dimensional network structure is removed while the three-dimensional structure is substantially maintained. Examples of the drying method include supercritical drying, freeze drying, vacuum drying, spray drying, microwave drying, hot air or hot air drying.

  The present invention can provide high-order aggregate particles of phenol resin microspheres with a low content of ash, which can shorten the polymerization reaction and eliminate the pulverization step by the above production method.

  The high-order aggregate particles of the phenol resin microspheres of the present invention have a porous structure, filters for chemical industry, ion exchange resins, soundproofing materials, adsorbing materials for wastewater treatment and exhaust gas treatment, catalysts It can be used as a carrier, a radio wave absorber, an electrode material or the like.

It is also possible to produce higher-order aggregate particles of carbon microspheres by firing the higher-order aggregate particles of phenol resin microspheres of the present invention by a conventional method. Since the higher-order aggregate particles of the phenol resin microspheres of the present invention are not agglomerated, they can be transferred to the firing step without going through the pulverization step.
Firing is performed by a conventional method, for example, by heat treatment in a temperature range of 500 to 3000 ° C. in an inert gas atmosphere using a high-temperature treatment apparatus such as an electric furnace, a tubular furnace, or a box furnace. For example, nitrogen, argon, helium, or the like is used as the inert gas.

The average microsphere diameter of the carbon microspheres constituting the high-order aggregates of the carbon microspheres of the present invention is preferably in the range of 0.1 to 10 μm in that the specific surface area of the high-order aggregate particles can be increased.
The range is more preferably 0.2 to 8.0 μm, and particularly preferably 0.3 to 6.0 μm. When the average microsphere diameter of the carbon microspheres exceeds 10 μm, the higher-order aggregate particles become excessively large, and pulverization may be necessary depending on applications. The average microsphere diameter of the carbon microsphere can be calculated by the same method as the average microsphere diameter of the phenol resin microsphere.

  The average particle size of the high-order aggregate particles of the carbon microspheres of the present invention is preferably in the range of 0.1 to 1000 μm, more preferably in the range of 0.5 to 500 μm, from the viewpoint of handleability. The range of 0.1 to 100 μm is particularly preferable. When the average particle size of the high-order aggregate particles is less than 0.1 μm, the particles are likely to scatter and the handling property tends to be poor. When the average particle size exceeds 1000 μm, pulverization may be necessary depending on the application. is there. The average particle diameter of the high-order aggregate particles of the carbon microspheres can be calculated by the same method as the average particle diameter of the high-order aggregate of the phenol resin microspheres.

  The ash content of the high-order aggregate particles of the carbon microspheres of the present invention is preferably 2% by weight or less, more preferably 1% by weight or less, more preferably 0.1% by weight in terms of purity. It is particularly preferred. When the ash content exceeds 2% by weight, impurities may be eluted depending on the application, and the properties tend to be adversely affected. The ash content of the high-order aggregate particles of carbon microspheres can be calculated by the same method as that for the high-order aggregate particles of phenol resin microspheres.

  The high-order aggregate particles of the carbon microspheres of the present invention are promising as powdered carbon materials, for example, adsorbing materials, gas sensors, carbon supports for supporting catalytic metals, electrode supports for solar cells, lithium ion batteries, and capacitors. It is promising as an electrode material. In combination with techniques such as C / C composite, it can also be used for electromagnetic wave absorbers, and its industrial value is extremely high.

  EXAMPLES Next, the present invention will be described more specifically with reference to examples. However, this is merely an example and does not limit the present invention.

[Example 1]
Resorcinol (manufactured by Kanto Chemical Co., Inc.) 55 parts by weight, 37% formaldehyde aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) 81 parts by weight, and purified water (manufactured by Wako Pure Chemical Industries, Ltd.) 110 parts by weight are placed in a 1000 ml glass flask. The mixture was stirred at 30 ° C. with a stirrer at 150 rpm until the monomer was dissolved. Thereafter, 5 parts by weight of ammonium carbonate (Wako Pure Chemical Industries, Ltd.) was added. After the reaction solution became cloudy, the reaction temperature was raised to 60 ° C. and stirred for 2 hours. Further, the reaction temperature was raised to 90 ° C. and stirred for 2 hours. The obtained reaction solution was subjected to solid-liquid separation by a vacuum filtration method to obtain 80 parts by weight of high-order aggregate particles (hydrated material) of phenol resin microspheres.

  80 parts by weight of phenol resin microsphere high-order aggregate particles (water-containing product) were vacuum-dried at 50 ° C. to remove moisture, and 65 parts by weight of phenol resin microsphere high-order aggregate particles were obtained.

[Example 2]
A high-order aggregate of phenol resin microspheres was prepared in the same manner as in Example 1 except that 5 parts by weight of ammonium hydrogen carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of 5 parts by weight of ammonium carbonate. 60 parts by weight of particles were obtained.

[Example 3]
The phenol resin microspheres were operated in the same manner as in Example 1 except that 54 parts by weight of m-cresol (manufactured by Kanto Chemical Co., Inc.) was used instead of 55 parts by weight of resorcinol and 42 parts by weight of ammonium carbonate was used. As a result, 60 parts by weight of the higher-order aggregate particles were obtained.

[Example 4]
The operation was performed in the same manner as in Example 1 except that hot air drying was performed at 160 ° C. for 2 hours as a drying method to obtain 50 parts by weight of high-order aggregate particles of phenol resin microspheres.

[Comparative Example 1]
Resorcinol (manufactured by Kanto Chemical Co., Inc.) 55 parts by weight, 37% formaldehyde aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) 81 parts by weight, and purified water (manufactured by Wako Pure Chemical Industries, Ltd.) 110 parts by weight are placed in a 1000 ml glass flask. The mixture was stirred at 30 ° C. with a stirrer at 150 rpm until the monomer was dissolved. Thereafter, 5 parts by weight of sodium carbonate (Wako Pure Chemical Industries, Ltd.) was added. After the reaction solution became cloudy, the reaction temperature was raised to 60 ° C. and stirred for 2 hours. Furthermore, when the reaction temperature was raised to 90 ° C., it gelled during stirring and became a lump.

[Comparative Example 2]
Resorcinol (manufactured by Kanto Chemical Co., Inc.) 55 parts by weight, 37% formaldehyde aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) 81 parts by weight, and purified water (manufactured by Wako Pure Chemical Industries, Ltd.) 110 parts by weight are placed in a 1000 ml glass flask. The mixture was stirred at 30 ° C. with a stirrer at 150 rpm until the monomer was completely dissolved. Thereafter, 2 parts by weight of sodium carbonate (Wako Pure Chemical Industries, Ltd.) was added and stirring was continued. After 1 hour, stirring was stopped and the reaction solution was transferred to a 1000 ml plastic bottle and placed in a thermostatic bath at 30 ° C. After 24 hours, the temperature of the thermostatic bath was raised to 50 ° C. and left again for 24 hours. Thereafter, the temperature of the thermostatic bath was raised to 90 ° C. and left for 24 hours to obtain a black lump. This lump was vacuum dried to obtain 58 parts by weight of an organic polymer gel.

[Comparative Example 3]
Resorcinol (manufactured by Kanto Chemical Co., Inc.) 55 parts by weight, 37% formaldehyde aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) 81 parts by weight, and purified water (manufactured by Wako Pure Chemical Industries, Ltd.) 110 parts by weight are placed in a 1000 ml glass flask. The mixture was stirred at 30 ° C. with a stirrer at 150 rpm until the monomer was dissolved. Thereafter, 5 parts by weight of potassium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) was added. After the reaction solution became cloudy, the reaction temperature was raised to 60 ° C. and stirred for 2 hours. Furthermore, when the reaction temperature was raised to 90 ° C., it gelled during stirring and became a lump.

[Comparative Example 4]
Resorcinol (manufactured by Kanto Chemical Co., Inc.) 55 parts by weight, 37% formaldehyde aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) 81 parts by weight, and purified water (manufactured by Wako Pure Chemical Industries, Ltd.) 110 parts by weight are placed in a 1000 ml glass flask. The mixture was stirred at 30 ° C. with a stirrer at 150 rpm until the monomer was dissolved. Thereafter, 2 parts by weight of sodium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirring was continued. After 1 hour, stirring was stopped and the reaction solution was transferred to a 1000 ml plastic bottle and placed in a thermostatic bath at 30 ° C. A solution in which 300 parts by weight of cyclohexane (manufactured by Wako Pure Chemical Industries, Ltd.) and 30 parts by weight of sorbitan monooleate (SPAN80, manufactured by Aldrich) was separately prepared in a 2000 ml glass flask, and 12 hours passed. 30 parts by weight of the reaction solution in the thermostat was added dropwise, and the polymerization reaction was carried out at 25 ° C. for 3 days while stirring at 800 rpm. After completion of the reaction, the reaction solution was filtered and vacuum-dried to obtain 5 parts by weight of organic polymer gel spherical particles.

For the high-order aggregate particles of the phenol resin microspheres obtained in Examples 1 to 4 and the gel block or spherical particles obtained in Comparative Examples 1 to 4, the following items were evaluated and the results are shown in Table 1. .
(Ash content)
The ash content was measured by calcining 30 g of a sample in an air stream of 300 ml / min at 800 ° C. for 3 hours, measuring the weight of the residue after ashing, and calculating the ratio (% by weight) with respect to the weight of the sample before firing. .

(Average particle size)
The particle size distribution was calculated as 50% D of the particle size distribution measured using a laser light scattering particle size distribution analyzer (SALD-3000J, manufactured by Shimadzu Corporation).

(R (ave) value)
Randomly extract a sample, take a projection photograph of the whole particle with an electron microscope, measure the length of the longest diameter R1 and the shortest diameter R2 passing through the midpoint of the longest diameter R1, respectively. The ratio R2 / R1 was calculated. This R2 / R1 was defined as an R value, and an R (ave) value was obtained by calculating an average value for 100 samples.

(Average microsphere diameter)
Samples are extracted at random, and a projection photograph of the whole particle is taken with an electron microscope. The longest straight line connecting the two ends of the microspheres constituting the particles of the projected photograph is regarded as the diameter, and the diameters of all the microspheres appearing in the projected photograph are measured, and the average value is the average microsphere diameter. Calculated as

[Example 5]
50 parts by weight of the high-order aggregate particles of the phenol resin microspheres obtained in Example 1 were placed in a tube installed in a vacuum incinerator (VHL-gr 20/20/20 manufactured by Shimadzu Mectem), and nitrogen gas was supplied at a flow rate of 300 ml / The mixture was calcined at 700 ° C. for 2 hours while being circulated for minutes to obtain 29 parts by weight of high-order aggregate particles of carbon microspheres.

[Example 6]
The operation was performed in the same manner as in Example 5 except that the firing temperature was 2000 ° C., and 20 parts by weight of high-order aggregate particles of carbon microspheres were obtained.

[Comparative Example 5]
50 parts by weight of the lump obtained in Comparative Example 1 was pulverized with a cutter mill and placed in a tube installed in a vacuum incinerator (VHL-gr 20/20/20 manufactured by Shimadzu Mectem), and nitrogen gas was circulated at a flow rate of 300 ml / min. Then, the mixture was baked at 700 ° C. for 2 hours to obtain 23 parts by weight of a carbon gel.

For the high-order aggregate particles of carbon microspheres obtained in Examples 5 to 6 and the carbon gel obtained in Comparative Example 5, the same items as above were evaluated, and the results are shown in Table 2.

  In Examples 1 to 4, high-order aggregate particles of phenol resin microspheres with low ash content were obtained. In Examples 5 to 6, high-order aggregate particles of carbon microspheres having a low ash content were obtained.

It is an electron micrograph of the higher order aggregate particle of the phenol resin microsphere obtained in Example 1 of this invention. It is an electron micrograph of the higher order aggregate particle of the phenol resin microsphere obtained in Example 1 of this invention. It is an electron micrograph of the higher order aggregate particle | grains of the phenol resin microsphere obtained in Example 3 of this invention. It is an electron micrograph of the higher order aggregate particle | grains of the phenol resin microsphere obtained in Example 3 of this invention.

Claims (10)

  High-order aggregate particles of phenol resin microspheres, wherein the phenol resin microspheres form a three-dimensional structure.   When the ratio of the longest diameter R1 of the higher-order aggregate particles to the shortest diameter R2 passing through the midpoint of the longest diameter R1 is R2 / R1, the average value R (ave) of R2 / R1 is 0.95 or less. The higher-order aggregate particles of phenol resin microspheres according to claim 1, wherein:   3. The high-order aggregate particles of phenol resin microspheres according to claim 1, wherein an average microsphere diameter of the phenol resin microspheres is in a range of 0.1 to 10 μm.   The high-order aggregate particle of the phenol resin microsphere according to any one of claims 1 to 3, wherein an average particle size of the high-order aggregate particle is 0.1 to 1000 µm.   The high-order aggregate particle of the phenol resin microsphere according to any one of claims 1 to 4, wherein the ash content is 1% by weight or less.   A method for producing high-order aggregate particles of phenol resin microspheres, wherein a phenol and an aldehyde are polymerized in an aqueous medium in the presence of an ammonium salt.   The fine carbon particles obtained by firing the high-order aggregate particles of the phenol resin microspheres according to 1 to 5 above or the high-order aggregate particles of the phenol resin microspheres obtained by the production method according to 6 above at 500 to 3000 ° C. High-order aggregate particles of spheres.   The high-order aggregate particles of carbon microspheres according to claim 7, wherein an average particle diameter of the high-order aggregate particles is 0.1 to 1000 μm.   9. The high-order aggregate particles of carbon microspheres according to claim 7 or 8, wherein an average microsphere diameter of the carbon microspheres is in a range of 0.1 to 10 [mu] m.   The high-order aggregate particles of carbon microspheres according to any one of claims 7 to 9, wherein the ash content is 2% by weight or less.