JP2020055258A - Body containing fine particle group - Google Patents

Abstract

To provide a body containing fine particle group that is made from epoxy resin containing carbon fiber and contains fine particles with a particle size distribution, etc. that meets the demand.SOLUTION: The present invention is a body containing a fine particle group A selected from the "group consisting of film, nonwoven fabric, packing, fiber, anode, and paint" containing the fine particle group A of 1 μm to 30 μm and a body containing a fine particle group B of 3 μm to 120 μm selected from the "group consisting of sheets, paints, building materials, furniture, and housings of electrical products" containing the fine particle group B of 3 μm to 120 μm, and the inclusion of fine particles, wherein the fine particle group A is obtained in steps (1) to (4), and the fine particle group B is obtained in steps (1) and (2). (1) the process of obtaining a broad particle group F by using an airflow grinder 11; (2) the process of collecting the fine particle group B in a cyclone device 21; (3) the process of having a circulation device 31 and having the fine particle group A stay in a cyclone portion 23 and the circulation device; and (4) the process of weakening or stopping the operation of the circulation device 31 and the cyclone device 21 to collect the fine particle group A.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a fine particle group containing body containing a fine particle group having a defined particle size distribution. More specifically, the present invention relates to a specific particle group containing body containing "particles having a defined particle size distribution and particle size distribution" obtained by using a carbon fiber-containing epoxy resin as a raw material and pulverizing it by a specific method. is there.

Carbon fiber reinforced plastics (CFRP) (hereinafter sometimes abbreviated simply as “CFRP”) is a plastic containing carbon fiber as a reinforcing material in a matrix resin and has both strength and lightness. It is used for many purposes.
The CFRP can be obtained by dispersing and containing carbon fibers in a matrix resin such as an epoxy resin and heating the mixture under pressure or heating using a microwave or the like and molding.

  However, scraps produced by the above molding; prototypes including failed products; used molded products; etc., are harmful to carbon fibers; matrix resins are often thermosetting resins; carbon fibers Recycling is difficult for reasons such as separation of matrix and matrix resin; and, with a few exceptions (recycling), mainly landfill disposal.

For example, the following is known as the recycling method.
Patent Document 1 discloses a technique in which a matrix resin of CFRP is burned into a flake-like carbon fiber mass, and this and a new thermoplastic resin chip are kneaded while being melted, extruded, and then cut into pellets. Have been.
Patent Document 2 discloses a crushed waste carbon fiber reinforced plastic processed so as to have a fixed direction diameter as large as 3 mm or more and to have a specific radius of curvature.
Patent Document 3 discloses a method for treating waste plastic, in which a fiber reinforced plastic (FRP) chip and a thermoplastic plastic material are kneaded while being heated and melted, and then cooled and cured to obtain a dumpling-like solid containing fibers. Have been.
Patent Document 4 discloses a first step of producing a detoxifying material by heat-treating CFRP by burning a matrix resin, applying a sizing agent to the detoxifying material, and then pulverizing carbon fibers while kneading. There is disclosed a method of recycling CFRP, which comprises a second step of producing a recycled material by the method and a third step of pelletizing the recycled material.

However, the method of separating the carbon fiber and the matrix resin is extremely difficult by both the combustion treatment and the chemical treatment. Even if the separation can be performed, the separated carbon fiber is a harmful substance, and the separation increases the cost. As described above, landfill disposal has been mainly performed with CFRP as described above.
Even if CFRP is heated and melted together with a matrix resin, the matrix resin is often a thermosetting resin such as an epoxy resin, so that it has been difficult to recycle it as a useful material. In addition, even if the combustion treatment can render the carbon fiber harmless and the resulting treated product finer, the cost increase due to the burning treatment is unavoidable. there were.
Further, as described in Patent Document 2, for example, even if the material is crushed and recycled, its application range (use range and application) is extremely limited due to its size.

Patent Document 5 describes a “method of producing reclaimed filled fine particles” that converts unnecessary CFRP into fine particles having a wide range of application without exposing (detoxifying) carbon fibers by a specific grinding method. I have.
However, when trying to expand the application range (use) and application of the fine particles, the particle size distribution of the fine particles containing the fine particles is changed to “film, sheet, nonwoven fabric, fiber, casting, etc.” to which the fine particles are applied. It is necessary to optimize the structure according to the “structure” or “dispersion of paint or the like” (use range, use, etc.).
In some cases, it may be necessary to control (freely) the “proportion of carbon fiber and epoxy resin” in the fine particle group so that it is in a suitable range for the intended use.

  Although the demand for CFRP recycling is increasing, the above-mentioned known techniques require high production costs including pulverization and recovery for various re-uses; application range of recycled products (fine particles). Narrowness; residual harmfulness of carbon fiber; difficulty in controlling the particle size distribution while suppressing the cost of fine particles; difficulty in adjusting the “existence ratio of carbon fiber and epoxy resin” in fine particles or required for the adjustment It was insufficient for reasons such as high cost; and there was room for further improvement.

JP-A-7-118440 JP 2000-254919 A JP 2001-030245 A JP 2009-138143 A JP 2018-020500A

  The present invention has been made in view of the background art described above, and an object of the present invention is to solve the problem of carbon fiber exposure by using a carbon fiber-containing epoxy resin body which is a kind of carbon fiber reinforced plastic (CFRP) as a raw material. It is an object of the present invention to provide a variety of fine particle group-containing bodies containing "fine particle groups which can be obtained at a low cost without increasing the number of production steps and the like and have a particle size distribution and the like suitable for the intended use (demand)".

The present inventor has conducted intensive studies to solve the above-described problems, and as a result, using a specific pulverizer, and, after the pulverization, using a device having a specific cyclone site, if a specific process is performed, It has been found that classification can be performed into a plurality of specific fine particle groups.
The “at least two types of fine particle groups having different particle size distributions” obtained in this manner greatly expand the range of application (reuse) (application field; type of object such as sheet; etc.), The inventors have found that the above-mentioned problems can be solved, and have completed the present invention.

That is, the present invention
A fine particle group A-containing material selected from the group consisting of “film, nonwoven fabric, packing, fiber, negative electrode, and paint” containing fine particle group A having a particle size distribution of 1 μm or more and 30 μm or less,
The fine particle group A provides a fine particle group A-containing substance, which is obtained by a production method having all of the following steps (1) to (4).
(1) Broad particle group of carbon fiber-containing epoxy resin by using “air current crusher that has two or more impellers and crushes particles to be crushed by collision of swirling air current generated by rotation of the impellers”. (2) Transfer tube, "Cyclone device comprising cyclone part, damper, and final recovery container in this order from the side of the air-flow crusher" is sucked, and the above-mentioned crushing step (1) While transferring the broad particle group obtained in the above, into the cyclone site, the cyclone device is operated to collect the fine particles belonging to “fine particle group B having a particle size distribution of 3 μm to 120 μm” in the final collection container. B Recovery Step (3) Further, the cyclone apparatus further includes a step of “having an inlet between the outer peripheral inner wall of the cyclone portion and a central axis and being connected as an outlet in the middle of the transfer pipe. And the fine particles belonging to the fine particle group A are kept in the cyclone portion and the circulating device without being put in the final collection container during the operation of the cyclone device. Step (4) Close the damper, weaken or stop the operation of the circulating device, weaken or stop the operation of the cyclone device, and drop and collect the fine particle group A. Collection process

The present invention also includes a fine particle group B selected from “a group consisting of sheets, paints, building materials, furniture, and housings of electrical products”, which contains a fine particle group B having a particle size distribution of 3 μm or more and 120 μm or less. Body
The fine particle group B is provided by a production method having the following steps (1) and (2), and provides a fine particle group B-containing material.
(1) Broad particles of the carbon fiber-containing epoxy resin are obtained by using an “air current crusher that has two or more impellers and crushes particles to be crushed by a swirling air current generated by rotation of the impellers to crush the particles.” Pulverizing step for obtaining a group (2) The transfer pipe, “a cyclone device comprising a cyclone part, a damper, and a final recovery container in this order from the airflow crusher side” are sucked, and the crushing step (1) is performed. ), While moving the broad particle group obtained in step (c) into the cyclone site, by operating the cyclone apparatus to collect fine particles belonging to “fine particle group B having a particle size distribution of 3 μm to 120 μm” in the final collection container. Group B recovery process

  Hereinafter, the “fine particle group A” and the “fine particle group B” may be collectively referred to as “fine particle group”, and the “fine particle group A-containing substance” and the “fine particle group B-containing substance” may be collectively referred to as “fine particle group-containing substance”. Body ".

ADVANTAGE OF THE INVENTION According to this invention, the said problem and subject are solved, and the carbon-fiber-containing epoxy resin body of CFRP, which had to be mainly landfilled until now, can be reclaimed as a useful material at a sufficiently low cost.
That is, the fine particle group contained in the fine particle group-containing body of the present invention is subjected to the pulverization / classification object specializing in the carbon fiber-containing epoxy resin body, and in particular, the pulverization method and the classification method (combination) are special; Furthermore, the classification method is very special in that classification can be performed while collecting the fine particle group. As a result, it is possible to obtain preferable physical properties of the fine particles and a fine particle group having a preferable particle size distribution, and it is possible to suitably use the fine particles for various applications thereafter.
In particular, since the fine particle group is excellent as a filled particle or a dispersed particle, the fine particle group-containing body of the present invention containing the fine particle group is extremely superior in physical properties and the like.
Further, the fine particle group can be crushed and classified at low cost, and if necessary, can be adjusted at low cost to adjust the epoxy resin content (CER). Therefore, the present invention has extremely good matching properties from the viewpoint of recycling.

In addition, since a dangerous carbon fiber isolation step is not required, and the carbon fibers are not actually separated or liberated, the safety of the fine particle group is high, and therefore, the fine particle group-containing material of the present invention is high. Can be manufactured without any problem in safety.
The complete combustion treatment method for disposing of CFRP has a huge energy cost and cannot be reused. Further, a semi-combustion treatment method as a method of separating CFRP into carbon fibers and a matrix resin also requires an energy cost, and the chemical treatment method is a practical method because the matrix resin remains halfway. It has not been converted.
The fine particle group-containing material of the present invention is obtained by using CFRP as a raw material, which was not practically reusable conventionally. Therefore, it is extremely advantageous in terms of energy cost, and since the carbon fiber and the matrix resin are not positively separated in the first place, the danger of the carbon fiber cannot be a problem. In addition, since the carbon fiber and the matrix resin are not separated, it is extremely advantageous in terms of cost.

Further, in the technology of processing from a few hundred microns to a millimeter order or more to form a group of regenerated fine particles, the application of the regenerated product is extremely limited, so that it is not put to practical use, and after all, landfill disposal is better. It was the result of saying.
According to the present invention, a fine particle group having a particle size distribution of a part of the “particle size range of 1 μm or more and 120 μm or less” can be obtained easily and inexpensively while maintaining good physical properties. Therefore, the fine particle group-containing material of the present invention containing the fine particle group (fine particle group A or fine particle group B) has both good physical properties and simplicity and low cost. Further, since the fine particle group has a specific useful particle size distribution, the fine particle group-containing material obtained by filling and dispersing in a new binder resin has both good physical properties and simplicity and low cost.
In the fine particle group-containing material of the present invention, the carbon fiber contained therein is not too short, and retains "characteristics such as increased strength unique to carbon fiber".

  The fine particle group contained in the fine particle group A-containing body or the fine particle group B-containing body of the present invention has the following effects. Has good classification accuracy and suitable particle size distribution; manufacturing equipment is simple and no manufacturing cost is incurred; there is no exposure or release (desorption) of acicular carbon fibers, and detoxification is achieved Has been achieved; the carbon fibers are suitably embedded (coated) with an epoxy resin (the carbon fibers remain contained as well as the carbon fiber-containing epoxy resin before milling); a liquid dispersion medium ( Excellent dispersibility in paint solvents and the like and solid dispersion media (embedding resin, binder resin, etc.); fine particle group A having a particle size distribution suitable for each subsequent application And the fine particle group B; preferably, the “mass content ratio of the epoxy resin to the total weight of the fine particle group” (CER) is adjusted.

It is the schematic of the apparatus used for manufacture of the fine particle group contained in the fine particle group containing body of this invention, Comprising: (1) a grinding | pulverization process, (2) fine particle group B collection | recovery process, and (3) fine particle group A. It is a schematic diagram showing the aspect of a stay process. FIG. 2 is a schematic view of an apparatus used for producing a fine particle group contained in the fine particle group-containing body of the present invention, and is a schematic view showing an aspect of (4) a fine particle group A collecting step. It is a cross-sectional view of a cyclone part in a cyclone device, and is a schematic diagram showing a positional relationship of an “intake of particle group A” in a circulation device provided in the cyclone device. (1) It is a graph which shows the example of the typical particle size distribution of the broad particle group obtained by performing a grinding process. (2) It is a graph which shows the example of the particle size distribution of the fine particle group B obtained by performing the fine particle group B collection process. (4) A graph showing an example of the particle size distribution of the fine particle group A obtained by performing the fine particle group A collection step. It is a scanning electron microscope (SEM) photograph of a typical broad particle group. 4 is a scanning electron microscope (SEM) photograph of a typical fine particle group B. 5 is a scanning electron microscope (SEM) photograph of a typical fine particle group A. (1) It is sectional drawing which shows an example of the aspect of two impellers in the airflow crusher used in a grinding process.

  Hereinafter, the present invention will be described, but the present invention is not limited to the following specific embodiments, and can be arbitrarily modified within the scope of the technical idea. In addition, the present invention is divided into an aspect 1 and an aspect 2, and the features common to the aspects 1 and 2 will be collectively described below.

<Aspect 1 of the present invention>
Embodiment 1 of the present invention is a fine particle group A-containing material selected from “a group consisting of a film, a nonwoven fabric, a packing, a fiber, a negative electrode, and a paint” containing a fine particle group A having a particle size distribution of 1 μm or more and 30 μm or less. So,
The fine particle group A is a fine particle group A-containing substance obtained by a production method having all of the following steps (1) to (4).

(1) The carbon-fiber-containing epoxy resin is broadened using a “air-flow crusher 11 that has two or more impellers and crushes the particles to be crushed by the swirling airflow generated by the rotation R of the impeller to crush the particles.” Pulverizing step (2) for obtaining particle group F “Cyclone apparatus 21 including transfer pipe 22, cyclone site 23, dampers 24 and 25, and final recovery container 26 in this order from the side of airflow pulverizer 11” And the cyclone device 21 is operated while transferring the broad particle group F obtained in the above-mentioned pulverizing step (1) into the cyclone site, and “the fine particle group B having a particle size distribution of 3 μm or more and 120 μm or less”. (3) A fine particle group B collecting step of collecting fine particles belonging to the final collecting container 26 into the final collecting container 26 (3). A circulation device 31 "having an inlet 33 between the transfer tube 22 and being connected as an outlet in the middle of the transfer pipe 22". Particle group A staying step of staying in the cyclone portion 23 and the circulating device 31 without entering the collection container 26 (4) While closing the damper, weakening or stopping the operation of the circulating device 31, and Particulate group A collection step of reducing or stopping the suction S of the cyclone device 21 and dropping and collecting the particle group A

<Aspect 2 of the present invention>
Embodiment 2 of the present invention is directed to a fine particle group B selected from “a group consisting of sheets, paints, building materials, furniture, and housings of electric appliances”, containing fine particle groups B having a particle size distribution of 3 μm or more and 120 μm or less. The inclusion body,
The fine particle group B is a fine particle group B-containing material obtained by a production method having the following steps (1) and (2).

(1) The carbon-fiber-containing epoxy resin is subjected to “an airflow pulverizer 11 that has two or more impellers and pulverizes the particles to be pulverized by colliding target particles with a swirling airflow generated by rotation R of the impellers”. A pulverizing step (2) for obtaining the broad particle group F “a cyclone device 21 having the transfer pipe 22, the cyclone part 23, the damper, and the final recovery container 26 in this order from the side of the airflow pulverizer 11”. Then, while transferring the broad particle group F obtained in the pulverizing step (1) into the cyclone site, the cyclone device 21 is operated to belong to the “fine particle group B having a particle size distribution of 3 μm or more and 120 μm or less”. A fine particle group B collecting step of collecting fine particles in the final collecting container 26

<Aspect of fine particle group>
<< Epoxy resin body containing carbon fiber >>
In Embodiments 1 and 2 of the present invention, the “carbon fiber-containing epoxy resin body” refers to a structure in which carbon fibers are dispersed in “epoxy resin that is a matrix resin”.
It is essential that the matrix resin contains an epoxy resin, but other resins may be mixed therein. Examples of other resins include thermosetting resins such as unsaturated polyester resin, vinyl ester resin, phenol resin, cyanate ester resin, and polyimide resin; polyamide resin (PA), polycarbonate resin (PC), and polyphenylene sulfide resin (PPS). ), Thermoplastic resins such as polyetheretherketone resin (PEEK); and the like.

The "carbon fiber-containing epoxy resin body" used as a raw material in the first and second aspects of the present invention is not limited, but is preferably CFRP that is no longer required from the viewpoint of cost reduction.
Here, the term "CFRP that is no longer needed" refers to CFRP that is generally used and sold, which is no longer needed, CFRP that is waste, CFRP that has come out as a prototype (including failed products) by manufacturers, etc. Is mentioned. Specific examples include, but are not limited to, golf club shafts; tennis racket frames; fishing rods; automobile frames and various parts; airplane wings and various parts; Parts; musical instruments, cases of portable goods, etc .;

  The "carbon fiber-containing epoxy resin body" may be any of a prepreg containing carbon fibers in an epoxy resin and coexisting and heated under pressure in an autoclave, and a molded one obtained by heating using a microwave or the like. May be.

<< particle size distribution >>
Embodiment 1 of the present invention relates to a fine particle group A-containing body containing “fine particle group A having a particle size distribution of 1 μm or more and 30 μm or less”.
The particle group A must have a particle size distribution of 1 μm or more and 30 μm or less, but is preferably 1.3 μm or more and less than 20 μm, and particularly preferably 2 μm or more and 15 μm or less.
In addition, Embodiment 2 of the present invention relates to a fine particle group B-containing material containing “fine particle group B having a particle size distribution of 3 μm or more and 120 μm or less”.
The particle group B must have a particle size distribution of 3 μm or more and 120 μm or less, but preferably 3.3 μm or more and 90 μm or less, particularly preferably 4 μm or more and 60 μm or less.

Regardless of Embodiment 1 or Embodiment 2, as long as the particle size distribution is within the above range, it is easy to produce (pulverize / classify) in the steps described below, and the obtained fine particle groups are widely used.
Also, in both the fine particle group A and the fine particle group B, when the lower end of the particle size distribution is too small (tailed to the small particle size side), the length of the carbon fiber becomes short, and it becomes difficult to obtain strength or the like. The dispersibility / filling property is reduced; the scattering property is increased, and the operation such as measurement is difficult;
On the other hand, in both the fine particle group A and the fine particle group B, when the upper end of the particle size distribution is too large (when tailing to the large particle size side), the dispersibility / filling property is reduced.

In the fine particle group-containing body of the present invention, other fine particle groups may be contained in addition to the fine particle group A and the fine particle group B described above.
Examples of such “other fine particle group” include a fine particle group A ′ having a particle size distribution of 1 μm or more and 5 μm or less, preferably more than 1 μm and less than 5 μm, and particularly preferably 1.5 μm or more and 4 μm or less. . The “fine particle group A” can be conceptually divided into the “fine particle group A” and the “fine particle group A ′” and can be used separately for subsequent applications.

Further, in step (2) or in steps (2), (3), and (4), a dust collector such as a bag filter is provided from above the cyclone portion 23 without being retained in the cyclone device 21. The “ultrafine particle group P having a smaller particle size distribution than the fine particle group described above” obtained by the ultrafine particle collection device 41 is obtained, but the fine particle group containing body of the present invention may contain the ultrafine particle group P. Good.
The “ultrafine particle group P” also includes fine particles (group) substantially not containing carbon fibers or containing only a very small amount. In this case, even if the particle size is not smaller than that of the fine particle group A or the fine particle group B, it is included in the ultrafine particle group P as a definition.
The ultrafine particle group P can also be used for adjusting the “content ratio of epoxy resin to the entire fine particle group (CER)” (described later) of the fine particle group A or the fine particle group B.

The average particle size of the fine particle group A in the aspect 1 of the present invention is preferably 2 μm or more and 20 μm or less, more preferably 2.5 μm or more and 15 μm or less, and particularly preferably 3 μm or more and 10 μm or less.
In addition, the average particle size of the fine particle group B in aspect 2 of the present invention is preferably from 4 μm to 60 μm, more preferably from 7 μm to 50 μm, and particularly preferably from 10 μm to 40 μm.
When the average particle size is in the above range, it is easy to produce (pulverize / classify) in the steps described later, and the obtained fine particle groups are widely used. When the above range is deviated from the upper side or the lower side, the same thing as described in the place of the particle size distribution may occur.

In the present invention, “particle size distribution” refers to a range (μm) in which 80% by mass (volume%) or more of the fine particles fall.
The particle size distribution and the average particle size in the present invention are defined as those measured by a wet method using a laser diffraction / scattering type particle size distribution measuring device Microtrack manufactured by Nikkiso Co., Ltd. and measured by the measuring device (method). You.
The vertical axis of the particle size distribution in the present invention is mass (volume), and the “average particle size” refers to the volume (mass) average particle size measured by the above apparatus.

In the embodiment 1, the fine particle group contained in the fine particle group-containing body of the present invention is the fine particle group A produced by the production method having all of the steps (1) to (4) (FIGS. 1 and 2). ).
The fine particle group contained in the fine particle group-containing body of the present invention is the fine particle group B produced by the production method having the steps (1) and (2) in the second embodiment. The fine particle group B may be produced at the same time that the fine particle group A is produced by the production method having all of the steps (1) to (4). That is, the fine particle group B was collected in the step (2) while the fine particle group A was staying in the circulation device 31 or the cyclone site 23 in the step (3) using the apparatus as shown in FIG. (FIG. 1).
Hereinafter, the method for producing the fine particle group contained in the fine particle group-containing body of the present invention will be described step by step.

<Method for producing fine particles>
<< Crushing process >>
In the production of the fine particle group contained in the fine particle group-containing body of the present invention, the carbon fiber-containing epoxy resin body D may be prepared before (1) the pulverizing step in any of the first and second aspects. It is preferable to have a crushing step of crushing. In other words, before the carbon fiber-containing epoxy resin body D is charged into the airflow pulverizer 11, the carbon fiber-containing epoxy resin body D is crushed to a range allowable as a size to be charged into the airflow pulverizer 11, and “the crushed product E of the carbon fiber-containing epoxy resin body E Is preferable.
The apparatus used for the crushing is not particularly limited, and examples thereof include a cutter mill, a crusher mill, a hammer mill, and an axial flow mill.

The crushing size of the crushed material E depends on the airflow crusher 11 to be used, but as the maximum crossing length of the crushing object, a size in the range of 0.2 cm to 5 cm is preferable, and a size in the range of 0.5 cm to 3 cm is preferable. Particularly preferred.
If the input size to the airflow crusher 11 is too large, the airflow crusher 11 may not be crushed. On the other hand, if the input size to the airflow crusher 11 is too small, there is no need to reduce the size. In which the following characteristics of the airflow pulverizer cannot be used; in particular, the case where the carbon fiber and the epoxy resin are separated.

<< (1) grinding process >>

The “crushed product E of the carbon fiber-containing epoxy resin body” obtained in the above-mentioned crushing step is put into the airflow crusher 11 using the hopper 12 or the like, and the following (1) crushing step is performed (FIGS. 1 and 10). .
(1) In the pulverizing step, the carbon fiber-containing epoxy resin body is pulverized by pulverizing the carbon fiber-containing epoxy resin body by pulverizing the particles to be pulverized by a swirling airflow generated by rotation R of the impeller 14. This is a step of obtaining the broad particle group F using the “machine 11”.
Here, the "air flow pulverizer" refers to a device that generates an air flow by rotation R of an impeller (rotor blade) and pulverizes an object put in the air flow in a dry manner to produce fine particles.

It is preferable to obtain a broad particle group F having a particle size distribution of 1 μm or more and 120 μm or less, more preferably 1.3 μm or more and 90 μm or less, particularly preferably 2 μm or more and 60 μm or less by pulverizing with an airflow pulverizer 11. Is obtained.
Within this range, the particles are easily crushed by the airflow crusher 11, the carbon fibers are not exposed or released (separated), and the fine particle group A and the fine particle group B have the above-described effects. Further, if the lower end of the particle size distribution of the broad particle group F before classification is too small or the upper end is too large, the same as described in the above “Particle size distribution of fine particle group A or fine particle group B” is used. May occur.

When it has two or more impellers 14 and is pulverized by an air current generated by rotating the impellers 14 with a motor 13 or the like, it is easy to pulverize in the range of the above particle size distribution; carbon fibers are exposed on the surface of the pulverized fine particles. No and / or the carbon fibers are not released from the fine particles (group); mainly, the particles are crushed by the collision of the particles, so that the temperature rise of the target object is suppressed; Pulverized into an easy form; not by shearing with a metal blade, but mainly by collision between particles, so that the obtained fine particles (group) have very little metal contamination; CER [% by mass]) can be adjusted only by changing the conditions of the impeller;
In addition, the carbon fiber is suitably covered with the epoxy resin to stabilize the quality, and the release of the carbon fiber is suppressed, so that it is safe for workers, users, and the like.
Further, as a further application, when the obtained fine particle group A or fine particle group B is dispersed in a binder resin or a dispersion medium to produce a film, a sheet, a structure, a paint, or the like, the “fine particle group-containing material” Has an excellent effect to be described later.

  For example, when using a crusher mill, a pin mill, a cutter mill, a hammer mill, an axial mill, or the like, it is difficult to reduce the average particle diameter sufficiently while suppressing costs (for example, pulverizing until the main particle diameter becomes 120 μm or less). Difficult to obtain), the particles obtained by pulverizing with these pulverizers were obtained because the average particle size was too large, or the particle size distribution was too wide and the maximum particle size was too large ( (Fine) The application of the particles is limited, and an excellent fine particle group-containing material as in the present invention cannot be obtained. That is, there is almost no use of a structure (including a film, a sheet, etc.) or a dispersion (including a paint, etc.) obtained by filling or dispersing the obtained (fine) particles, and the range of application is extremely limited. .

For example, a crusher such as a rotary collision type, a roll type, a media type, a stone mortar type, and a cutter type that collides with a rotating body, applies impact, compression, friction, shearing, etc. to a carbon fiber-containing epoxy resin body to be crushed. Since the mechanical stress is excessively applied, it is difficult to sufficiently reduce the (average) particle size, and the “effect when using the airflow pulverizer” cannot be obtained for the obtained fine particles.
On the other hand, a jet mill or the like, which crushes an object by colliding the object with a collision plate, can reduce the average particle size to a sufficiently small value, but the needle-like carbon fibers are exposed or separated, and the crushing operator or the obtained fine particle group Is extremely dangerous for some users. Further, there is a case where the pulverization processing efficiency (speed) is too low to increase the cost.

The airflow pulverizer 11 is used for pulverizing foodstuffs / feedstuffs containing components such as starch and protein that are easily degraded by heat, components that easily emit fragrance by heat, and components that easily adhere to the inside of the pulverizer by heat. Are particularly preferably used.
In the (1) pulverization step of the present invention, the airflow pulverizer used for pulverizing foodstuffs, feeds, and the like uses a particle size distribution, an average particle diameter, a pulverization processing efficiency (speed), a pulverization target It is particularly preferable in terms of suppressing the temperature rise of the object.

  As the airflow crusher 11, a commercially available device can also be suitably used. Commercial products include, for example, a cyclone mill manufactured by Shizuoka Plant Co., Ltd., a cyclone mill manufactured by Shizuoka Machinery Co., Ltd., a super powder mill manufactured by Nishimura Machinery Co., Ltd., a tornado mill manufactured by Sanjo Industry Co., Ltd., and Furukawa Soki Dream Mill manufactured by Systems Co., Ltd., and the like.

The present invention provides the following formula (1) by increasing or decreasing the rotation speed or the peripheral speed of the impeller 14 and / or increasing or decreasing the impeller interval L between the two impellers 14 in the step (1). It is preferable that the above-mentioned fine particle group is manufactured by decreasing or increasing the epoxy resin content (CER [% by mass]) represented by the formula (1).
Here, the above "raise or lower", "expand or narrow" and "decrease or raise" have the same order for all three before and after the "or".
CER [% by mass]
= 100 x [mass of epoxy resin in particle group (g) / [mass of particle group (g)] ... (1)

  In the present invention, the above fact has been newly found. That is, the existing carbon fiber-containing epoxy resin body D can be pulverized while arbitrarily adjusting the CER to a suitable value for the fine particle group-containing material. As a result, a suitable fine particle group-containing material containing the fine particle group was obtained.

FIG. 10 shows a schematic view of an example of the airflow pulverizer 11 having two impellers 14.
The number of the impellers 14 provided in the airflow crusher 11 is preferably two or more from the viewpoint of the crushing efficiency, and two impellers 14 among them can be rotated in the same direction or in the opposite direction. You may.

The rotation speed of the impeller 14 depends on the diameter of the impeller 14, but when an impeller having a diameter of 150 mm to 600 mm is used, it is preferably 3000 rpm to 14000 rpm, more preferably 4000 rpm to 12000 rpm, and more preferably 5000 rpm to 10000 rpm. Preferred (FIG. 2).
The peripheral speed of the impeller 14 hardly depends on the diameter of the impeller 14, and is preferably from 60 m / s to 300 m / s, more preferably from 80 m / s to 260 m / s, and particularly preferably from 100 m / s to 220 m / s. (FIG. 2).

  The distance D between the two impellers 14 is preferably adjusted within the range of 15 mm to 60 mm for pulverization, more preferably 18 mm to 50 mm, and particularly preferably 20 mm to 40 mm (FIG. 2). Within the above range, a good swirling airflow can be easily generated in the apparatus, and efficient pulverization can be performed. In particular, CER can be easily adjusted to any suitable value (range).

If the rotation speed and the peripheral speed of the impeller 14 are too slow and / or the impeller interval L between the two impellers 14 is too narrow, the particles cannot be sufficiently crushed, especially the particle size cannot be made sufficiently small (for example, 120 μm or less). In some cases, the CER may become too large.
On the other hand, when the rotation speed and the peripheral speed of the impeller 14 are too fast and / or the impeller interval L between the two impellers 14 is too wide, the production (crushing) efficiency is too low, and the operation cost is too high. , Time and cost may be wasted, and the CER may be too small.

In the present invention, the fine particle group preferably has an epoxy resin content (CER [% by mass]) of 0.5% by mass or more and 15% by mass or less.
Fine particle groups having such a CER range can be suitably obtained by adjusting the conditions of the impeller using the airflow pulverizer 11.
The CER of the fine particle group contained in the fine particle group-containing material of the present invention is more preferably 1% by mass to 14% by mass, further preferably 2% by mass to 13% by mass, and particularly preferably 3% by mass or less. It is not less than 12% by mass and not more than 12% by mass.

  Although it depends on the content of the epoxy resin in the carbon fiber-containing epoxy resin body D as a raw material, various fine particle groups can be suitably produced while controlling the CER within the above-mentioned CER. Wide; good in filling properties into binder resin and good dispersibility in dispersion medium in use; useful in exposing and isolating carbon fibers from fine particles. The fine particle groups having different CERs can be selectively used depending on (use of) the fine particle group-containing substance of the present invention.

  When the fine particles (group) are manufactured by pulverization as described above, the CER of the obtained fine particles is determined as “the epoxy resin contained in the carbon fiber-containing epoxy resin body D used as a raw material”, “the carbon fiber-containing epoxy resin”. It is usually smaller than the content ratio to "whole body". Therefore, in other words, since the CER of the fine particle group can be reduced, the range of application when the fine particle group-containing body is manufactured by newly adding a binder resin or the like to the obtained fine particle group is expanded.

  The operation method of the airflow crusher 11 may be a continuous charging (continuous feed) method or a batch (batch) method. In the case of the continuous charging method, the charging speed (feed speed) of the carbon fiber-containing epoxy resin body to be crushed is set. ) Is preferably 0.5 [(kg / min) / L] or more and 3 [(kg / min) / L] or less, preferably 1 [(kg / min) / L] per volume (L) of the airflow pulverizer. It is more preferably at least 2.5 [(kg / min) / L] and particularly preferably at least 1.5 [(kg / min) / L] and 2 [(kg / min) / L].

  When the charging speed is too high, there are cases where the pulverization cannot be performed sufficiently, particularly when the particle size cannot be sufficiently reduced (for example, 70 μm or less). In addition, when the charging speed is too slow, the production (crushing) efficiency is too low, the operation cost is too high, and the time and cost are wasted.

  Although not particularly limited, the airflow pulverizer 11 has a classifying function inside, and the classified coarse powder is pulverized again inside the airflow pulverizer 11, and the classified fine powder is mixed with the broad particle group F. Is preferably transferred to the cyclone device 21 from the viewpoint of removing coarse powder, giving a suitable particle size distribution to the broad particle group F to be subjected to the step (2) and subsequent steps, and the like.

During the pulverization, the upper limit of the temperature of the object to be pulverized (the carbon fiber-containing epoxy resin body D, the pulverized product thereof, and the broad particles (group)) is preferably maintained at 70 ° C. or lower, more preferably 60 ° C. or lower, and more preferably 50 ° C. or lower. C. or lower, more preferably 40.degree. C. or lower. If the temperature is too high, the effect of using the airflow crusher 11 may not be obtained.
The lower limit of the temperature is not particularly limited, and is preferably room temperature at the time of pulverization. That is, 0 ° C. or higher is preferable, and 10 ° C. or higher is particularly preferable.

As shown in FIG. 7, the broad fine particles (group) obtained as described above are rounded due to the impact at the time of pulverization using the airflow pulverizer 11, rather than being fibrous or acicular. FIG. 8 shows the shape of a typical fine particle (group) B, and FIG. 9 shows the shape of a typical fine particle (group) A. The fine particle (group) A and the fine particle (group) B also have the shape of the fine particle. Are rounded as in the case of the broad fine particles (group) before classification (after step (1)).
At the time of pulverization by the airflow pulverizer 11, the epoxy resin in the carbon fiber-containing epoxy resin body D extends on the surface of the carbon fiber so as to coat the surface of the carbon fiber, and embeds and covers the carbon fiber. Most of them are held without being separated from the carbon fibers. Therefore, the effects of the present invention described above are exhibited.

<< (2) Particle group B recovery step >>
In the step (2), the “cyclone device 21 including the transfer pipe 22, the cyclone part 23, the dampers 24 and 25, and the final recovery container 26 in this order from the airflow crusher 11” is sucked. By operating the cyclone device 21 while transferring the broad particle group F obtained in the pulverizing step (1) into the cyclone part 23, the fine particles belonging to the fine particle group B are collected in the final collection container 26. This is a particle group B recovery step.

Since the fine particle group A in the aspect 1 of the present invention (the fine particle group A-containing substance) is collected in the “(4) Fine particle group A collection step” described below, the fine particle group B obtained in the above step (2) is necessary. Absent.
Therefore, in the first aspect of the present invention, the step (2) is performed to remove relatively large fine particles belonging to “fine particle group B having a particle size distribution of 40 μm or more and 70 μm or less”.
In Embodiment 1 of the present invention, the fine particle group B obtained in the step (2) can be pulverized again to obtain the fine particle group A, or can be stored and stored in the second embodiment of the present invention (fine particle group A-containing substance). Can be used or can be discarded, but it is preferable to use it for aspect 2 of the present invention (containing fine particle group A).
On the other hand, in the aspect 2 of the present invention (the fine particle group B-containing material), the fine particle group B obtained in the above step (2) is used.

  As shown in FIGS. 1 and 2, the transfer pipe 22 is a pipe for transferring the broad particle group F pulverized by the airflow pulverizer 11 to the cyclone device 21. It is connected to the upper part of the part 23. A “particle group A circulation pipe 35 of the circulation device 31” described later is connected to the transfer pipe 22 on the way, and the particle group A merges with the broad particle group F immediately after pulverization at the outlet 34 to form a cyclone. It returns to the upper part of the part 23.

The size of the cyclone portion is not particularly limited, but the diameter of the central portion of the height of the cyclone portion is preferably 50 mm or more and 700 mm or less, more preferably 70 mm or more and 300 mm or less, and particularly preferably 100 mm or more and 200 mm or less. The height of the cyclone portion is preferably from 100 mm to 1600 mm, more preferably from 130 mm to 700 mm, and particularly preferably from 200 mm to 400 mm. The volume of the cyclone site is preferably from 0.03 L to 600 L, more preferably from 0.3 L to 100 L, and particularly preferably from 1.5 L to 15 L. If the size is too small, the feeding (feed) speed to be described later may decrease and productivity may decrease. If the size is too large, the fine particle group A and the fine particle group B may not be suitably divided.
It is also preferable to increase the collection speed by arranging a plurality of cyclone devices 21 in parallel.

The cyclone device 21 is operated, and the cyclone device 21 is sucked by the suction S. As schematically shown in FIGS. 1 and 2, in the cyclone portion 23, heavy particles such as the above-described fine particle group B are pressed against the outer periphery (near) of the cyclone by centrifugal force by the cyclone mechanism, and the cyclone portion 23 is formed. It falls while rotating (circulating) along the outer circumference toward the lower part of.
On the other hand, the light particles such as the fine particle group A and the ultra fine particle group P move downward near the center axis 27 of the cyclone portion 23 after falling down the cyclone portion 23. Among the fine particles moved to the upper part, the above-mentioned ultra fine particles pass through the cyclone portion 23 upward as they are and are collected by the ultra fine particle collecting device 41 having the dust collector 42.

  (2) In the fine particle group B collection step, the damper located below the cyclone portion 23 is opened as an open damper 24, and the fine particles that have fallen around the cyclone portion 23 during (full) operation (suction S). The group B is collected in the final collection container 26.

  The supply (feed) speed of the broad fine particle group to the cyclone device 21 (because the steps (1) and (2) are continuous), the feed rate (feed rate) of the raw material in the above-mentioned (1) pulverization step It is almost the same as Further, since the size and the suction force (suction capacity) of the cyclone portion 23 provided in the cyclone device 21 are almost constant, it is preferably from 2.5 kg / min to 20 kg / min, and preferably from 4 kg / min to 13 kg / min. Is more preferable, and 8 kg / min or more and 10 kg / min or less are particularly preferable.

  Since the particle size distribution of the broad particle group F supplied to the cyclone device 21 is 1 μm or more and 120 μm or less as described above, the particle size distribution of the fine particle group B that falls down the cyclone portion 23 and is collected in the final collection container 26 Can be 3 μm or more and 120 μm or less. If the airflow crusher 11 has a classifying function and the upper limit of the particle size is set to, for example, 70 μm, the upper limit of the particle size distribution of the broad particle group F and the fine particle group B can be set to, for example, 70 μm.

<< Ultra fine particle collection process >>
The present invention further has a bag filter in the middle of suctioning the cyclone device 21 and collects ultrafine particles P having a particle diameter of less than 3 μm (the particle diameter may be large when no carbon fiber is contained). It is preferable to have an ultrafine particle group recovery step.
Among the fine particles that have moved to the upper part of the cyclone part 23 during the (full) operation, the ultrafine particles that have penetrated the cyclone part 23 upward as they are are collected by the ultrafine particle collection device 41 provided with the dust collector 42. The ultrafine particles may be discarded or reused.

<< (3) Particle Group A Staying Step >>
In the step (3), the cyclone apparatus 21 further includes an inlet 33 between the outer peripheral inner wall of the cyclone portion 23 and the central shaft 27 and is connected as an outlet 34 in the transfer pipe 22. A circulation device 31 ", and allows the fine particles belonging to the fine particle group A to stay in the cyclone portion 23 and the circulation device 31 during the operation of the cyclone device 21 without entering the final collection container 26. This is the particle group A staying step.
Usually, the step (3) is performed simultaneously with the step (2) in terms of time.

  As shown in FIGS. 1, 2 and 3, the cyclone device 21 used in the present invention has “an intake port 33 between the outer peripheral inner wall of the cyclone portion 23 and the central shaft 27, A circulating device 31 "which is connected as an outlet 34. FIG. 3 shows the positional relationship between the central axis 27 of the cyclone portion 23, the inner peripheral wall, and the intake port 33.

  During operation of the cyclone device (full), suction is performed by the blower 32 provided in the circulating device 31, the fine particle group A is taken in from the intake port 33 of the circulating device 31, and an outlet 34 provided in the middle of the transfer pipe 22. Is discharged into the transfer pipe 22 to be combined with the just-crushed broad fine particles.

During operation of the cyclone device (full), the fine particles belonging to the fine particle group B are collected in the final collection container 26 below the cyclone portion 23 as described above, while the fine particles belonging to the fine particle group A are light (full). ) During the operation, the cyclone device 31 is circulated in the circulation device 31. In step (4) described later, when the suction S (operation) of the cyclone device 21 is weakened or stopped, the cyclone device 21 falls outside the cyclone portion for the first time.
That is, since the particle group A has a particle size distribution of 1 μm or more and 30 μm or less and is lighter than the particle group B having a particle size distribution of 3 μm or more and 120 μm or less, the particle group A falls in the cyclone portion in the step (2). Thereafter, it is hard to be recovered in the final recovery container 26 thereunder, and rises again near the central axis 27 of the cyclone portion 23 (see FIG. 1).

  The circulation device 31 guides the rising fine particles belonging to the fine particle group A to the transfer pipe 22 again by the blower 32, combines the fine particles with the broad particle group F, and re-enters the cyclone device 21, whereby the cyclone device ( During the (full) operation, the fine particle group A is constantly circulated in the cyclone device 21 and stays there. The “hatched portion (hatched portion) in the transfer pipe 22 and the blower 32” in FIG. 1 indicates a place where the particle group A circulates and stays in the circulating device 31.

On the other hand, the ultra-fine particle group P, which is smaller than the particle group A, is not sucked from the intake port 33 of the circulating device 31 (not taken into the circulating device 31), and the cyclone portion 23 is removed during the operation of the cyclone device. It penetrates upward and exits toward the ultra-fine particle collection device 41 having the dust collector 42.
That is, in the steps (2) and (3), during the operation of the cyclone device (full), the particle group B is collected in the final collection container 26, and the ultra particle group P penetrates upward through the cyclone part 23 and the ultra particle collection device 41 And the fine particle group A having a particle size distribution intermediate between them is circulating in the circulation device 31.

As shown in FIG. 3, the intake 33 of the circulation device 31 is located between the inner peripheral wall of the cyclone part 23 and the central axis 27. The position of the inlet 33 is not particularly limited as long as the fine particle group A can be efficiently circulated, but is preferably 1/10 or more and 2/3 or less of the radius R from the central axis side to the outer peripheral inner wall from the central axis side. , 以上 or more and 以下 or less, more preferably １ ／ or more and ３ or less.
If the intake 33 is too close to the central axis 27 (when the above value is small), it is determined that “the ultrafine particles (including carbon fibers) that want to penetrate upward near the central axis of the cyclone portion 23 and go to the ultrafine particle collection device 41. (In some cases, large particles having a particle diameter of 1 μm or more may be included) "may be taken into the circulation device 31 and mixed into the particle group A.
On the other hand, when the inlet 33 is too far from the central axis 27 and approaches the outer periphery (when the above value is large), the “particles that should be circulated as the particle group A in the step (3) and collected for the first time in the step (4)” In the case where “A” penetrates upward through the cyclone site 23 and exits toward the ultra-fine particle collecting device 41, or conversely, “the fine particle group B to be collected in the step (2)” is introduced into the circulation device 31. In some cases, it is mixed with the fine particle group A.

The “position of the cyclone portion 23 in the vertical direction” of the intake 33 of the circulation device 31 is 以上 or more from the bottom of the entire “height of only the inclined portion of the cyclone portion 23” ( It is preferably 10/10 (the uppermost meaning) from the 1/2 position, more preferably 3/5 or more and 9/10 or less, particularly preferably 2/3 or more and 7/8 or less.
If the intake port 33 is too low (the value is too small), the diameter of the cyclone portion 23 is too small, so that the fine particle group B, the fine particle group A, and the ultrafine particle group P may not be clearly separated. On the other hand, even if the intake 33 is too high (even if the above value is too large), there is a case similar to the above.

<< (4) Particle Group A Collection Step >>
In the step (4), the damper is closed, the operation of the circulation device 31 is weakened or stopped, and the suction S of the cyclone device 21 is weakened or stopped, and the fine particle group A is dropped. This is the step of collecting the fine particle group A to be collected (FIG. 2).

  As shown in FIG. 2, when approaching the end of the (full) operation of the cyclone device 21, the damper located below the cyclone portion 23 is closed to form a closed damper 25, and the suction S of the cyclone device 21 is weakened or stopped. The operation of the circulation device 31 is weakened or stopped by weakening or stopping the blower 32 of the circulation device 31. Here, it is preferable that the above-mentioned “weak” or “stop” is gradually weakened, especially for the suction S, and finally stopped. Until the blower 32 is stopped, the suction S is performed at a suction force of preferably 10% or more and 40% or less at full operation, particularly preferably 15% or more and 25% or less, and gradually stopped finally. preferable.

  After the damper is closed, the fine particle group B collected in the final collection container 26 is taken out or stored together with the final collection container 26.

  Thereafter, the above operation is performed to collect the fine particle group A. After collecting the fine particle group B in the final collection container 26, an empty container (which may be the same as or different from the final collection container 26) for collecting the fine particles A is installed, and The collected fine particle group A may be collected, or the fine particle group A may be directly dropped and collected in the container without temporarily collecting on the closed damper 25.

<Particles containing fine particles>
The fine particle group A and the fine particle group B in the present invention are useful as an anti-slip member, an antistatic member, a visible light blocking member, an ultraviolet blocking member, a strength reinforcing member, a flame retardancy imparting member, a coloring member, a waterproof member and the like.
In addition, since it has many excellent physical properties due to carbon fiber, it can be reused for products and applications where carbon fiber itself has already been used (products composed of CFRP, applications of CFRP). it can.

What is generally used as carbon fiber reinforced plastic (CFRP) is also preferred as the fine particle group-containing material of the present invention. That is, the particles can be regenerated using the fine particles as the filler particles.
As such, specifically, (a part of) sports equipment such as, for example, golf club shafts, tennis racket frames, fishing rods; various parts of vehicles such as automobiles, bicycles, airplanes, and ships; Musical instruments, portable goods, and fragile cases; and the like.

Embodiment 1 of the present invention provides a fine particle group A-containing material selected from “a group consisting of a film, a nonwoven fabric, a packing, a fiber, a negative electrode, and a paint” containing the fine particle group A having a particle size distribution of 1 μm or more and 30 μm or less. It is.
Further, the aspect 2 of the present invention is directed to a fine particle selected from “a group consisting of a sheet, a paint, a building material, furniture, and a housing of an electric product” containing the fine particle group B having a particle size distribution of 3 μm or more and 120 μm or less. Group B inclusions.

  In the above-mentioned films, sheets, structures, etc., in addition to the fine particle group and the binder resin, a plasticizer for the binder resin, a dispersant for the fine particles, a heat stabilizer, a foaming agent, a colorant, a lubricant, a charge, It may contain an inhibitor, a conductive material, another inorganic or organic filler, a flame retardant / flame retardant, a surfactant, a release agent, a thickening stabilizer, and the like. Each of these may be used alone or in combination of two or more.

The fine particles of the present invention can be dissolved and dispersed in a dispersion medium together with a binder to obtain a dispersion such as a paint. In the case where the fine particle group-containing material of the present invention is in the form of a dispersion such as a paint, or the fine particle group-containing material of the present invention is in the form of a dispersion such as a film, a nonwoven fabric, and a building material, and the state of the dispersion at the stage of production thereof In this case, the dispersion preferably contains at least the above-described fine particle group, dispersant, binder, dispersion medium, and the like of the present invention.
The content of the fine particle group in the dispersion is optional depending on the intended conductivity and application, but is preferably from 0.1 to 40% by mass, more preferably from 1 to 30% by mass, based on the total mass of the dispersion. Is more preferable, and 2 to 20% by mass is particularly preferable.

The fine particle group A and the fine particle group B may be various kinds of fine particle group inclusion bodies by adding a binder in addition to a raw material-derived epoxy resin (raw material matrix resin) contained therein (residual). Can be.
Once a base such as a sol compound is prepared, a fine particle group is added thereto and stirred, and the obtained “fine particle mixed sol compound” is applied and heated to obtain a sheet as a fine particle group-containing body.

Such a binder is not particularly limited. For example, hard or soft polyvinyl chloride; polyvinylidene chloride; thermoplastic polyurethane; polyamide; polyester (polyethylene terephthalate, polybutylene terephthalate, etc.); polysulfone; polycarbonate; ethylene vinyl acetate copolymer (EVA). ), Polyethylene, polypropylene, poly (meth) acrylate, polystyrene, polyacetal, vinyl (co) polymers such as fluororesins; silicone resins; In addition, thermoplastic resins such as the above homopolymers and copolymers can be used.
Further, a thermosetting resin such as an epoxy resin, an unsaturated polyester, a phenol resin, a polyimide, a urea resin, a melamine resin, and a urethane resin may be used.
In addition, biological polymers such as cellulosic polymers, proteins (such as gelatin and casein), polypeptides and polysaccharides, and derivatives thereof are also included.

  The mass of the binder is preferably from 20 to 5,000 parts by mass, more preferably from 40 to 2,000 parts by mass, particularly preferably from 70 to 1,000 parts by mass, per 100 parts by mass of the fine particle group. If the amount of the binder is too small, the binding properties between the fine particles and the binder may decrease, and if the amount is too large, the physical properties of the carbon fiber such as conductivity may decrease.

The dispersant is not particularly limited, and includes any of a cationic surfactant, an amphoteric surfactant, and an anionic surfactant.
In addition, a polymer dispersant such as a salt of a (meth) acrylic acid (co) polymer, (carboxymethyl) cellulose (salt), and a known dispersant having no repeating unit may also be used.

  The amount of the dispersant required for dispersion varies depending on the amount and specific surface area of the contained fine particles, but is preferably 5 to 200 parts by mass, more preferably 10 to 120 parts by mass with respect to 100 parts by mass of the fine particles. 20 to 70 parts by mass are particularly preferred. If the amount of the dispersant is too small, it may be difficult to disperse the fine particle group.On the other hand, if the amount is too large, if conductivity is required, the contact between the fine particles is inhibited, and the conductivity is reduced. There is.

<<< Production method of fine particle group containing body >>>
The method for producing the fine particle group-containing body of the present invention is not particularly limited and is determined in consideration of the structure and physical properties of the binder resin and the like, and a known method can be used. It is also preferable to prepare a compound containing a binder resin, a plasticizer, a dispersant, and the like in advance at the stage, and blend the fine particles of the present invention therein. It is also preferable to mix some of the above components in advance and then mix and mix the other components. It is also preferable to dissolve and disperse in a solvent / dispersant before mixing.

  Known devices can be used for dispersing, mixing, kneading, and the like of the fine particle group in a binder, a dispersion medium, and the like, and are not limited. Examples thereof include (vibration) a media mill such as a ball mill, a bead mill, and a sand mill; Sound waves) Stirring devices such as a homogenizer, a magnetic stirrer, a homomixer, and a ribbon mixer; roll mills such as two rolls and three rolls; rotary homogenizers; attritors; paint shakers; it can.

As a method of molding the fine particle group-containing body, for example, molding without a solvent; distilling and drying the solvent or the dispersant after coating with a solvent or a dispersant; heating and melting the binder and pouring it into a mold. It is preferably manufactured by cooling and taking out later; spray molding; trowel coating; Further, baking may be performed after such molding and coating film formation.
As the application method, specifically, for example, spray coating, dip coating, spin coating, knife coating, roll coating, kiss coating, gravure coating (gravure printing), screen printing, intaglio printing, inkjet printing, pad printing, And the like.

  In the case where the fine particle group-containing substance is produced by coating on a substrate such as a film or a sheet, a wetting agent is used for the purpose of improving the wettability prior to the application on the substrate surface. Is also preferred. Examples of the wetting agent include, but are not limited to, lower alcohols such as methanol and ethanol; surfactants; and the like.

The type of the substrate is not particularly limited, and examples thereof include resin and glass. Examples of the resin include polyesters such as polyethylene terephthalate (PET) and polylactic acid; polycarbonates (PC); vinyl resins such as polymethyl (meth) acrylate (copolymer), styrene-butadiene copolymer, and polyvinyl chloride; polyimides; Polyphenylene sulfide; aramid; polyolefin-based resins such as polypropylene and polyethylene; cellulose-based resins; Examples of the glass include soft glass, hard glass, quartz glass, and Pyrex (registered trademark).
The substrate surface is preferably treated by corona discharge, plasma treatment or the like, and it is also preferable to provide an undercoat layer on the substrate surface.

<< Containing body of fine particle group A >>
In the aspect 1 of the present invention, the film has a thickness of 40 μm or less, an electromagnetic wave shielding film, an electronic substrate shielding cover film, a conductive film, a metal oxidation preventing film, an agricultural mulching film, a transparent member smoke film, or It is preferable that the fine particle group A-containing material is an antistatic film.
Since the particle size distribution of the fine particle group A is 1 μm or more and 30 μm or less, it can be suitably filled and used in the film having a thickness of 40 μm or less. The thickness of the film is more preferably 1 μm or more and 35 μm or less, and particularly preferably 1.5 μm or more and 30 μm or less.

Since the carbon fiber has conductivity, the fine particle group A functions as an antistatic member, and is filled with an electromagnetic wave shielding film, an electronic substrate shielding cover film, a conductive film, a metal oxidation preventing film, or an antistatic film. Suitable as particles.
In addition, since the carbon fiber is black, the fine particle group A functions as a visible light blocking member, an ultraviolet blocking member, a coloring member, and the like, and is suitable as a filling particle for an agricultural mulching film or a smoke film for a transparent member.
In addition, since the carbon fiber is excellent in slip resistance, strength, and waterproofness, the fine particle group A is suitable as filler particles for all the films.

In the aspect 1 of the present invention, it is preferable that the nonwoven fabric is the above-mentioned fine particle group A-containing body which is a nonwoven fabric for agriculture or a nonwoven fabric for a speaker.
Since the carbon fibers are black and endothermic and are dispersed to increase the strength, the fine particle group A is preferably contained in an agricultural non-woven fabric or a speaker non-woven fabric.

In the aspect 1 of the present invention, it is preferable that the packing is a packing for waterproofing electric material, and the fiber is the fine particle group A-containing body, which is a fiber for an insect repellent net.
Since carbon fibers are excellent in waterproofness, strength, and jet-blackness, the fine particle group A is preferably contained in packing for waterproofing electric materials or fibers for insect-proof nets.

Aspect 1 of the present invention is the fine particle group A-containing material, wherein the electrode is a negative electrode (anode) for a fuel cell, a negative electrode (anode) for a lithium secondary battery, or a negative electrode (cathode) for an electrolytic cell. Is preferred.
Since carbon fibers are excellent in electronic conductivity and have a graphite structure (layer structure), the fine particle group A is used as a graphite substitute as a fuel cell anode (anode), a lithium secondary battery anode (anode), or It is preferable to include it in the negative electrode (cathode) for the electrolytic cell.

In the aspect 1 of the present invention, it is preferable that the paint is the above-mentioned fine particle group A-containing material which is a conductive paint, an antistatic paint, or an antioxidant paint.
Since carbon fibers have conductivity, the fine particle group A functions as a conductive member or an antistatic member, and is suitable as a dispersed particle of a conductive paint, an antistatic paint, or an antioxidant paint.

  Among the fine particle group A, the fine particle group having a large particle size of 5 μm or less (distributed on the small particle size side) (such as the fine particle group A ′ having a particle size distribution of 1 μm or more and 5 μm or less) is particularly an electromagnetic wave shielding film. It can be particularly preferably used as filler particles for films such as electronic substrate shielding cover films, conductive films, and films for preventing metal oxidation.

<<< fine particle group B-containing body >>>
Embodiment 2 of the present invention is the fine particle group B-containing material, wherein the sheet is a conductive sheet, a heat conductive sheet, a snow melting sheet, a ground heating sheet, an anti-slip sheet, or an antistatic sheet having a thickness of 2000 μm or less. Preferably, there is.
Since the particle size distribution of the fine particle group B is 3 μm or more and 120 μm or less, it can be suitably filled and used in the above-mentioned sheet having a film thickness of 2000 μm or less.
The thickness of the sheet is more preferably 3 μm or more and 1000 μm or less, further preferably 4 μm or more and 300 μm or less, and particularly preferably 5 μm or more and 120 μm or less.

Since the carbon fibers are conductive, the fine particle group B is suitable as a conductive sheet or a filling particle of an antistatic sheet.
In addition, since carbon fibers are excellent in jet-blackness, heat-absorbing property, and strength, the fine particle group B is suitable as filler particles for a heat conductive sheet, a snow melting sheet, and a ground heating sheet (such as a livestock hut).
In addition, since the carbon fiber is excellent in anti-slip properties, strength, and the like, the fine particle group B is suitable as filler particles for an anti-slip sheet.

In the aspect 2 of the present invention, it is preferable that the paint is the above-mentioned fine particle group B-containing material which is a rust preventive paint, an anticorrosive paint, or a heat resistant paint.
Since carbon fibers are excellent in rust prevention / corrosion resistance and heat resistance, the fine particle group B is suitable as a rust prevention coating, a corrosion protection coating, or a heat resistance coating.

Embodiment 2 of the present invention is the fine particle group B-containing material, wherein the building material is a reinforced building material by forged composite (casting press method) or a lightweight and reinforced plate by extrusion molding, and the furniture is furniture with rails. Is preferred.
Since the carbon fiber has a function of increasing the strength, the fine particle group B is suitable as a casing of an electric product or a filler particle for the structure.

<<< Performance of the particle group containing body >>>
The fine particle group-containing material of the present invention has the various excellent functions described above, but the fine particle group is well dispersed; the aggregation of the fine particles (group) is suppressed; Excellent in electrical conductivity, antistatic properties, jet-blackness, heat absorption, anticorrosion, suitability for extrusion molding, etc .; when the fine particle group is a sheet or film, it does not crack even when it is folded; fine particles Bleeding of carbon fibers on the surface of the group inclusion is suppressed, and it is difficult to contaminate articles, limbs, clothes, etc., which are in contact with the surface, with black.

<About the product-by-process invention>
As described above, when the carbon fiber-containing epoxy resin body D is pulverized by the airflow pulverizer 11, the objects to be pulverized collide with each other to produce fine particles having a rounded surface. In addition, there are few carbon fibers exposed on the surface, and there is no mixing of metal elements derived from the pulverizer. In addition, since the temperature rise during pulverization is small, it is considered that the fine particles are unique.
However, it is impossible to directly specify the shape of such fine particles with parameters or the like, and it is not possible to directly specify the form of the carbon fiber exposed on the surface or to quantify the trace amount of contained metal. Impossible or almost impractical.

In addition, the manufacturing process in the present invention has a great feature that no cost is required, and the fine particle group manufactured in the process (1) (2) or the process (1) to (4) has a particle size. The distribution is optimal for a variety of applications and is not necessarily too sharp.
The CER usually changes from that of the carbon fiber-containing epoxy resin body D used as a raw material, and the content ratio between the fine particle group A and the fine particle group B is usually different, and also differs for each fine particle.
However, it is impossible or almost impractical to directly specify the particle size distribution of such a fine particle group or the component composition of the fine particles.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples as long as the gist of the present invention is not exceeded. In the following examples, Example 3 is omitted.

Example 1
<Crushing process>
From the carbon fiber reinforced plastic (CFRP) which has been a waste material, 5 kg of the carbon fiber-containing epoxy resin body is about 0.7 cm to about 2 cm by using a cutter mill (manufactured by Makino Sangyo Co., Ltd., small low-speed crusher GSL). Crushed to a corner.
Here, the carbon fiber-containing epoxy resin body D used as a raw material is obtained by forming a carbon fiber into a plate-like layer, infiltrating a thermosetting epoxy resin as a matrix resin therein, and thermosetting under pressure. And 85 parts by mass of carbon fiber and 15 parts by mass of a thermosetting epoxy resin. Next, a fine particle group A, a fine particle group B, and an ultrafine particle group P were manufactured in the following steps using the apparatuses shown in FIGS.

<(1) Grinding process>
The obtained “crushed product containing 85 parts by mass of carbon fibers and 15 parts by mass of a thermosetting epoxy resin” was charged into a crusher using a hopper 12 or the like as shown in FIG. As a pulverizer, an air current pulverizer (Cyclone Mill 400S, manufactured by Shizuoka Plant Co., Ltd.) is used, and pulverization is performed at room temperature (25 ° C.) under standard conditions of the air current pulverizer. Obtained.

The airflow pulverizer 11 has two impellers 14 having a diameter of 150 mm inside the apparatus. Large particles are coarsely pulverized by the first impeller and moved to the second impeller side. 1. In the (high-speed) swirling airflow around the second impeller, they collide with each other and are pulverized. That is, the particles to be pulverized mainly collide with each other by the swirling airflow to pulverize the particles (FIGS. 1 and 10).
Further, the airflow crusher 11 has a classification function inside the apparatus, and the classified coarse powder is crushed again inside, and the classified fine powder can be taken out, that is, the classification is performed by centrifugal force. The fine powder thus obtained was taken out by the airflow of the blower.

During the pulverization, the interval between the two impellers 14 of the airflow pulverizer was set to 30 mm, the rotation speed of the impeller 14 was 8000 rpm, and the peripheral speed at that time was 170 m / s (FIG. 10).
The collision between the particles to be pulverized and the impeller 14 is small, and since the particles are mainly pulverized by collision between the particles and cooled by a large amount of airflow, the temperature rise of the particles during the pulverization is suppressed. I couldn't see it.

FIG. 4A shows the particle size distribution of the obtained broad fine particle group. The particle size distribution of the obtained broad fine particle group (range in which 80% is included) was 1 μm or more and 120 μm or less. The broad particle group F had a volume average particle size of 40 μm. FIG. 4B shows the particle size distribution of the broad fine particle group similarly obtained by using another CFRP than in Example 1.
The particle size distribution and the average particle size in the present invention are defined as those measured by a wet method using a laser diffraction / scattering type particle size distribution measuring device Microtrack manufactured by Nikkiso Co., Ltd. and measured by the measuring device (method). You. All are distributions or average particle diameters based on volume (mass).

The carbon fibers of the carbon fiber-containing epoxy resin body D as the raw material were not exposed on the surface of the obtained fine particles, and the carbon fibers were covered with the epoxy resin (FIGS. 7 to 9).
Further, from the beginning to the end of the pulverization, the fibrous carbon fibers were not separated and taken out (discharged) from the airflow pulverizer 11.

<(2) Particle group B recovery step>
Using the “cyclone device 21 having the circulation device 31” as schematically shown in FIG. 1, the fine particle group B (fine particles belonging to the fine particle group) was collected in the final collection container 26 from the broad particle group F obtained above. .

The cyclone device 21 was equipped with the transfer pipe 22, the cyclone part 23, the closed damper 25, and the final recovery container 26 in this order from the side of the airflow crusher 11.
Further, the cyclone device 21 had a circulation device 31 having an intake 33 (for the particle group A) in the middle of the cyclone portion 23 (see FIGS. 1 and 3). The diameter at the midpoint of the height of the cyclone site was 150 mm, the height was 300 mm, and the volume was 5.3 L.

  The broad particle group F obtained in the pulverizing step (1) was supplied to the cyclone device 21 at a rate of 3 kg / min. The pulverizing speed was adjusted to such a speed, and the broad particle group was transferred from the airflow pulverizer 11 in the step (1) to the cyclone device 21 in the step (2) by the transfer pipe 22.

  The circulation device 31 was operated, and the particle group A was absorbed by the blower 32 and kept in the circulation device 31, while the particle group B was collected in the final collection container 26.

FIG. 5A shows the particle size distribution of the obtained fine particle group B. The particle size distribution of the fine particle group B (the range where 80% is included) was 3 μm or more and 60 μm or less. FIGS. 5B and 5C show the particle size distributions of broad fine particles obtained in the same manner using CFRP different from that in Example 1.
FIG. 8 shows a scanning electron microscope (SEM) photograph of the fine particle group B.

  The ultrafine particle group P that could not be collected by the cyclone device 21 was collected in an ultrafine particle group collection step using a bag filter.

<(3) Particle group A staying process>
The (3) particle group A staying step was performed in parallel with the (2) particle group B collection step.
The cyclone device 21 had "a circulating device 31 having, for example, an intake port 33 at a position as shown in FIG. 3 and being connected in the middle of the transfer pipe 22". The vertical position of the intake 33 was 2/3 from below the cyclone part 23.

  The suction S was performed to operate the cyclone device 21 to collect the particle group B in the final collection container 26, and at the same time, the particle group A was kept in the cyclone part 23 and the circulation device 31. That is, the fine particles A were sucked by the blower 32, returned to the transfer pipe 22 from the circulation inlet 33, combined with the broad fine particles from the airflow crusher 11, and then re-entered into the cyclone portion 23.

<(4) Particle group A collection step>
When the cyclone device 21 is fully operated for 60 minutes continuously and the particle group A is considered to be staying in the circulating device 31 and the cyclone portion 23 of about 50 kg, the damper is closed. Then, the output of the suction S of the cyclone device 21 was reduced to 20% of the full operation, and the suction of the blower 32 of the circulation device 31 was stopped (FIG. 2).

The collected fine particle group B was stored in the final collection container 26, and a container for collecting the fine particle group A was set in the same place.
The damper was changed to the open damper 24, and the particle group A accumulated on the damper and the particle group A existing in the cyclone device 21 including the circulation device 31 were collected in the container (FIG. 2).

FIG. 6 shows the particle size distribution of the obtained fine particle group A. The particle size distribution of the fine particle group A was 1 μm or more and 30 μm or less.
FIG. 9 shows a scanning electron microscope (SEM) photograph of the fine particle group A.

  The ultrafine particle group P that could not be collected by the cyclone device 21 was collected in an ultrafine particle group collection step using a bag filter. The particle size distribution of the ultrafine particle group P was 1 μm or less, or contained substantially no carbon fiber.

At this time, 10 kg of the fine particle group B, 50 kg of the fine particle group A, and 0.5 kg of the ultra fine particle group were obtained.
It was found that particles having different particle size distributions (fine particle group A and fine particle group B) can be produced depending on the use of the fine particle group.

<Repeat of steps (1) to (4)>
In order to avoid staying (circulating) a large amount of the particle group A in the apparatus, in order to collect the particle group A in the final collection container 26 in each case, the steps (1) to (3) are performed in three batches. (4) was performed. That is, the above steps were repeated three times to obtain the fine particle group B, the fine particle group A, and the ultrafine particle group P each having a total of 2.7 times the mass described above.

Example 2
Using a carbon fiber-containing epoxy resin body D containing 85% by mass of carbon fiber and 15% by mass of epoxy resin, which is a recycled carbon fiber reinforced plastic (CFRP), using the apparatus shown in FIGS. A fine particle group B was produced in the same manner as in Example 1, except for the conditions for the impeller 14.
That is, (1) In the pulverizing step, the conditions relating to the impeller 14 were varied in the following three stages to produce three types of fine particle groups B. However, the condition of the impeller of << condition 2 >> was the same as in Example 1.

<< Condition 1 >>
Rotation speed: 10000 rpm
Peripheral speed: 209 [m / s]
Impeller gap: 40mm
<< Condition 2 (same as Example 1) >>
Rotation speed: 8000 rpm
Peripheral speed: 168 [m / s]
Impeller gap: 30mm
<< Condition 3 >>
Rotation speed: 5000 rpm
Peripheral speed: 105 [m / s]
Impeller gap: 20mm

The “epoxy resin content (CER)” of the resulting fine particle group B is shown below.
In condition 1, R is not more than 2.5% by mass. In condition 2, R is not more than 7.0% by mass. In condition 3, R is not more than 12% by mass.

The same operation as described above was repeated five times while changing the batch, and the range of “epoxy resin content (CER)” was determined. The results are shown below.
In condition 1, R is 0.5% by mass or more and 5% by mass or less In condition 2, R is 5% by mass or more and 10% by mass or less In condition 3, R is 10% by mass or more and 15% by mass or less

  It was found that the content ratio (R) of the epoxy resin covering the carbon fiber can be adjusted according to the use of the fine particle group A and the fine particle group B.

Comparative Example 1
The pulverization was performed in the same manner as in Example 1 except that a crusher mill, a pin mill, a cutter mill, a hammer mill, or an axial mill was used in place of the airflow pulverizer 11 used in Example 1, but each was pulverized. Under the usual grinding conditions of the apparatus, it was difficult to grind to a particle size of 120 μm or less. In addition, attempts were made to form fine particles over a long period of time, but the temperature of the particles was excessively increased, or the particles could not be suitably pulverized. In addition, there were particles having no rounded particle shape and exposed carbon fibers. Therefore, it was not possible to produce a suitable fine particle group A and fine particle group B.

Comparative Example 2
The pulverization was performed in the same manner as in Example 1 except that a jet mill was used instead of the airflow pulverizer 11 used in Example 1. Although the particle size distribution of the broad fine particle group was almost the same as that of Example 1, the cost was increased because the pulverization efficiency was extremely poor.
In addition, since the carbon fibers were exposed or the carbon fibers became fibrous and were taken out (discharged), even sampling was dangerous, and fine particles could not be produced without danger, and there was no danger. Fine particles could not be produced.

Comparative Example 3
In the cyclone device 21 used in Example 1, the same operation as in Example 1 was performed except that the circulation device 31 was not provided, or (3) the fine particle group A staying step was not performed.
Only 1/10 of the fine particle group A was obtained in Example 1, and the fine particle group could not be recovered (substantially) to the extent that it could be put to practical use. Further, the particle size distribution of the fine particle group B almost coincided with the particle size distribution of the broad fine particle group charged, that is, the fine particle group B contained fine particles having a small particle size and could not be used as the fine particle group B. . That is, classification could not be suitably performed.

Comparative Example 4
A vibrating sieve classifier was used in place of the cyclone device 21 used in Example 1.
Classification took time (poor classification efficiency), and was not at all applicable in the field of recycling. In addition, the particle size distribution of the fine particle group A and the fine particle group B has a wide application range (where the particle group having the particle size distribution is used in many types of films, sheets, and structures), and the respective application ranges. In this case, the particle size distribution of the fine particle group A and the fine particle group B could not be adjusted appropriately.

Example 4
<< Production of Structure Containing Fine Particle Group A or Fine Particle Group B >>
A sol compound having the following formulation containing "polyvinyl chloride having a polymerization degree of 860 obtained by emulsion polymerization" as a binder resin was prepared. Hereinafter, polyvinyl chloride may be abbreviated as “PVC”. Hereinafter, the “particle group A or the particle group B” may be simply abbreviated as the “particle group”.

[Sol compound formulation]
Binder resin: Paste resin of PVC (degree of polymerization 860) 100.0 parts by mass Plasticizer: Diisononyl Phthalate (DINP) 35.0 parts by mass Dispersant: Higher fatty acid type, sorbitan monooleate 0.5 parts by mass Dispersant : Aliphatic hydrocarbon / carboxylic acid derivative carboxylic acid-based dispersant (BYK5125, manufactured by BYK) 0.5 part by mass Blowing agent: azodicarbonamide (manufactured by Otsuka Pharmaceutical Co., Ltd.) 2.0 parts by mass

30 parts by mass of the fine particle group A or the fine particle group B (each fine particle group) obtained in Example 1 was added to 100 parts by mass of the sol compound, and the mixture was stirred for 30 seconds with a mixer.
The stirred “fine particle mixed sol compound” was coated on paper with a thickness of 0.8 mm, placed in a normal air oven, and heated (baked) at 200 ° C. for 60 seconds, and foamed to a thickness of 2 mm. . Next, by cooling to room temperature, a 2 mm-thick “structured foam foamed sheet (layered) foamed PVC sheet” containing each fine particle group was obtained.

Evaluation example 1
The structure (sheet) obtained in Example 4 was evaluated as follows. The evaluation results are also described below.

<Dispersibility>
The evaluation was performed in the state of a “fine particle mixed sol compound”.
A double groove grind meter manufactured by Daiyu Co., Ltd. was used to check for any aggregates.
As a result, there was no aggregate, and the particle size distributions of the fine particle groups A and B were each maintained.

<Bubble burn, discoloration, uneven color>
A test piece (150 mm × 150 mm × 2 mm in thickness) of the structure (sheet) was visually observed from above.
As a result, any of foaming burn, discoloration, and color unevenness could not be confirmed. No burning due to heat storage was observed. The coarse particles in which the fine particles were aggregated could not be detected visually.
The center and four corners of the sheet were measured with a colorimeter manufactured by Konica Minolta, Inc.
As a result, the color difference ΔE was within 0.2 (a color difference that cannot be determined with the naked eye).

<Color development>
Regarding the color development of the structure (sheet), a fixed color development (color development from black to dark gray) was obtained by adjusting the content of fine particles and the like and controlling the color tone for each lot.

<Fragility>
A test piece (150 mm × 150 mm × 2 mm thick) of the structure (sheet) was bent outward by 90 ° to check whether a crack was formed on the surface.
As a result, four cracks having a length of 3 mm were confirmed at the center, but it was determined that there was no problem because the cracks were not normally bent by 90 °.
If there is non-dispersion even in a normal processed pigment, such pinholes and cracks caused by such pinholes are generated, so it was considered that there was no problem in the fine particles themselves.

<Bleedability>
A "sol compound sheet" for evaluation was prepared in the same manner as in the structure (sheet) of Example 4, except that a mirror surface iron plate was used and a sol compound containing no fine particles was prepared.
A test piece (150 mm × 150 mm × 2 mm in thickness) of the structure (sheet) which is the foamed PVC sheet obtained in Example 4 was sandwiched between the sheets, and heated and pressed at 60 ° C. using a pressing machine at 120 ° C. For 10 minutes, a weight of 10 kgf was applied.
After release, it was confirmed whether or not the black color of the carbon fibers in the fine particles in the structure (sheet) of Example 4 was transferred to the sol compound sheet.
As a result, no black color was visually observed.

Example 5
<Evaluation of Filling Particles for “Film with Thickness of 40 μm” of Fine Particle Group A>
5 parts by mass of the fine particle group A obtained in Example 1, 1 part by mass of a sodium salt of carboxymethyl cellulose, 1 part by mass of a sodium salt of a polymethacrylic acid copolymer, and 15 parts by mass of a styrene-methacrylic acid copolymer. The mixture was charged into 70 parts by mass of N-methyl-2-pyrrolidone as a solvent, stirred with a magnetic stirrer, and then dispersed with a ball mill for 3 hours.
The resulting dispersion was applied on a polyethylene terephthalate (PET) film using a bar coater to a dry film thickness of 40 μm, and dried at 80 ° C. (solvent was distilled off) to obtain a conductive film. .

  The obtained conductive film had a large surface conductivity, and was useful as an electromagnetic wave shielding film, an electronic substrate shielding cover film, a metal oxidation preventing film, and an antistatic film.

Example 6
<Evaluation of Filling Particles for “Film with Thickness of 40 μm” of Fine Particle Group A>
A dispersion liquid was obtained in the same manner as in Example 5, except that "15 parts by mass of the styrene-methacrylic acid copolymer" in Example 5 was changed to "15 parts by mass of the main component of the epoxy resin".
Thereafter, 3 parts by mass of a curing agent of an epoxy resin was added, and the mixture was sufficiently stirred, and then applied on a polyimide film using a bar coater to a dry film thickness of 40 μm to obtain a conductive film.

  The obtained conductive film was extremely useful as an electromagnetic wave shielding film, an electronic substrate shielding cover film, a film for preventing metal oxidation, an antistatic film, a transparent conductive film, and the like because of its large surface conductivity.

Example 7
<Evaluation of Filling Particles for “Film with Thickness of 40 μm” of Fine Particle Group A>
The used amount (parts by mass) of the fine particle group A obtained in Example 1 was appropriately adjusted, and the fine particle group A was dispersed by using polypropylene as a binder, heating without solvent, and kneading with three rolls.
The film was cast to a film thickness of 40 μm and cooled to obtain a film.

The resulting film was black, absorbing solar heat, and not transmitting sunlight, thereby suppressing the growth of weeds, and was useful as an agricultural mulching film.
Further, by reducing the amount (parts by mass) of the fine particle group A, it was useful as a smoke film for a transparent member.

Example 8
<Evaluation of Fine Particle Group A as Filled Particles for "Fibers and Nonwovens">
5 parts by mass of the “fine particle group A obtained in Example 1” was kneaded with 20 parts by mass of polyethylene terephthalate, and then fiberized according to a conventional method to obtain a fiber. The obtained fiber was useful as a fiber of a nonwoven fabric to be described later, as a fiber for an insect-proof net, and the like.

  The fiber obtained above was made into a nonwoven fabric according to a conventional method. Since the nonwoven fabric had high mechanical strength and blackness, it was useful as a heat insulating nonwoven fabric for agricultural use and a nonwoven fabric for speakers.

Example 9
<Evaluation of fine particle group A as packing particles for packing>
The fine particle group A obtained in Example 1 was heated and kneaded with a silicone resin to obtain a packing for waterproofing electric materials. The obtained packing for waterproofing electric materials had excellent strength and water resistance.

Example 10
<Evaluation of Fine Particle Group A as Negative Electrode (Material)>
The fine particle group A obtained in Example 1 was added to a carbonaceous material (such as graphite particles) and molded to obtain a negative electrode of a lithium ion secondary battery. Since a suitable conductive network can be formed, by using it as a negative electrode, a lithium ion secondary battery having excellent battery characteristics can be provided.

  The above electrode is useful as a negative electrode (anode) for a lithium secondary battery, and also useful as a negative electrode (anode) for a fuel cell, a negative electrode (cathode) for an electrolytic cell, and the like.

Example 11
<Evaluation of Fine Particle Group A as Dispersed Particles in Paint>
The dispersions of Examples 5 and 6 containing the fine particle group A obtained in Example 1 can be used as a paint or a base material of the paint.

7 parts by mass of the fine particle group A obtained in Example 1, 1 part by mass of a sodium salt of carboxymethyl cellulose, 1 part by mass of a sodium salt of a polymethacrylic acid copolymer, 15 parts by mass of a novolak-type epoxy oligomer, and After stirring 4 parts by mass of silica powder with a stirrer, the mixture was dispersed in a ball mill for 3 hours.
The resulting dispersion is mixed with an epoxy curing agent and applied to a substrate. The resulting film exhibits excellent conductivity, waterproofness, and strength. It was extremely useful as a paint, a waterproof paint and the like.

Example 12
<Evaluation of Fine Particle Group A as Dispersed Particles in Paint>
A dispersion was obtained in the same manner as in Example 11, except that toluene diisocyanate was used instead of the novolak-type epoxy oligomer of Example 11.
The resulting dispersion is mixed with a curing agent containing a polyhydric alcohol and applied to a substrate, and the resulting film exhibits excellent conductivity, waterproofness, and strength. It was useful as an antioxidant paint, an antioxidant paint, a waterproof paint and the like.

Example 13
<Evaluation of fine particles B as “filled particles” for “sheet having a thickness of 70 μm”>
5 parts by mass of the fine particle group B obtained in Example 1, 1 part by mass of a sodium salt of carboxymethyl cellulose, 1 part by mass of a sodium salt of a polymethacrylic acid copolymer, and 15 parts by mass of a styrene-methacrylic acid copolymer. The mixture was charged into 70 parts by mass of N-methyl-2-pyrrolidone as a solvent, stirred with a magnetic stirrer, and then dispersed with a ball mill for 3 hours.
The obtained dispersion was applied onto a polyethylene terephthalate (PET) film using a bar coater so as to have a dry film thickness of 70 μm, and dried at 80 ° C. (the solvent was distilled off) to obtain a sheet.

The obtained sheet was useful as a conductive sheet, an antistatic sheet, and the like because of its large surface and bulk conductivity.
In addition, the obtained sheet is excellent in thermal conductivity and mechanical strength, and is excellent in absorbing radiant heat because it is black, so it is extremely useful as a heat conductive sheet, snow melting sheet, ground heating sheet, slip prevention sheet, etc. Was useful.

Example 14
<Evaluation of fine particles B as “filled particles” for “sheet having a thickness of 70 μm”>
A dispersion was obtained in the same manner as in Example 13, except that “15 parts by mass of the styrene-methacrylic acid copolymer” in Example 13 was changed to “15 parts by mass of the main component of the epoxy resin”.
Thereafter, 3 parts by mass of a curing agent of an epoxy resin was added, and after stirring well, a sheet having a thickness of 70 μm was obtained.

The obtained sheet was useful as a conductive sheet, an antistatic sheet, and the like because of its large surface and bulk conductivity.
In addition, the obtained sheet is excellent in thermal conductivity and mechanical strength, and is excellent in absorbing radiant heat because it is black, so it is extremely useful as a heat conductive sheet, snow melting sheet, ground heating sheet, slip prevention sheet, etc. Was useful.

Example 15
<Evaluation of fine particles B as “filled particles” for “sheet having a thickness of 70 μm”>
Using the fine particle group A obtained in Example 1 and polypropylene as a binder, heating without solvent and kneading with a three-roll mill, the fine particle group B was dispersed to obtain a sheet having a thickness of 70 μm according to a conventional method.

  The obtained sheet is black, absorbs radiant heat, is excellent in strength, and is inexpensive, and thus was extremely useful as a snow melting sheet, a ground heating sheet, an anti-slip sheet, an antistatic sheet, and the like.

Example 16
<Evaluation of Fine Particle Group B as Dispersed Particles in Paint>
The dispersions of Examples 13 and 14 containing the fine particle group B obtained in Example 1 can be used as a paint or a base material of the paint.

Further, 7 parts by mass of the fine particle group B obtained in Example 1, 15 parts by mass of a novolak type epoxy oligomer, and 4 parts by mass of sedimentable barium sulfate were stirred by a stirrer, and then dispersed by a ball mill for 3 hours.
By mixing (by combining) the obtained dispersion with an epoxy curing agent, excellent rust preventive paint, anticorrosive paint, heat resistant paint and the like can be provided.

Example 17
<Evaluation of Fine Particle Group B as Dispersed Particles in Paint>
A dispersion was obtained in the same manner as in Example 16, except that toluene diisocyanate was used instead of the novolak-type epoxy oligomer of Example 16.
By mixing the obtained dispersion with a curing agent containing a polyhydric alcohol, excellent rust preventive paints, anticorrosive paints, heat-resistant paints and the like could be obtained.

Example 18
<Evaluation of fine particle group B as packing particles for housings of building materials, furniture, and electrical products>
By using styrene-butadiene rubber, elastomer, polyurethane, polyamide, polyphenol, polyester, and polycarbonate as binders, reinforced building materials and automotive materials such as “Forged Composites (registered trademark), casting press method”, and “furniture” , "Electric product housing" was obtained.
They can be extruded, and have achieved weight reduction, high strength, and low cost.

The fine particle group in the present invention does not substantially contain bare carbon fibers, and has excellent safety and physical properties because its surface is coated with an epoxy resin which was a matrix resin of CFRP. By blending or dispersing in a dispersion medium, it can be regenerated as a useful substance.
The useful materials include films, sheets, non-woven fabrics, packing, fibers, negative electrodes, paints, building materials, furniture, housings of electric appliances, and the like, and thus the present invention is widely used in the fields of production and use thereof. Things.
Further, the fine particle groups A and B in the present invention each have a suitable particle size distribution having a wide field of application, and can also be regarded as a black pigment, a processed pigment, an extender pigment, a filler, and the like. It is widely used in the fields of the above-mentioned structures and dispersions which are filled or dispersed.

DESCRIPTION OF SYMBOLS 11 Air flow crusher 12 Hopper 13 Motor 14 Impeller 21 Cyclone device 22 Transfer pipe 23 Cyclone part 24 Open damper 25 Closed damper 26 Final collection container 27 Central axis 31 Circulating device 32 Blower 33 Intake port 34 Exit 35 Particle group A circulation pipe 41 Super Particle collection device 42 Dust collector A Particle group A
B Particle group B
P Ultrafine particle group P
D Epoxy resin body containing carbon fiber E Crushed product of epoxy resin body containing carbon fiber F Broad particle group R Radius S Suction L Impeller spacing R Impeller rotation

Claims (14)

A fine particle group A-containing material selected from the group consisting of “film, nonwoven fabric, packing, fiber, negative electrode, and paint” containing fine particle group A having a particle size distribution of 1 μm or more and 30 μm or less,
The fine particle group A-containing body, wherein the fine particle group A is obtained by a production method having all of the following steps (1) to (4).
(1) Broad particle group of carbon fiber-containing epoxy resin by using “air current crusher that has two or more impellers and crushes particles to be crushed by collision of swirling air current generated by rotation of the impellers”. (2) A cyclone device comprising a transfer pipe, a cyclone part, a damper, and a final recovery container in this order from the side of the airflow crusher is sucked into the crushing step (1). While transferring the broad particle group obtained in the above, into the cyclone site, the cyclone device is operated to collect the fine particles belonging to “fine particle group B having a particle size distribution of 3 μm to 120 μm” in the final collection container. B Recovery Step (3) Further, the cyclone apparatus further includes a step of “having an inlet between the outer peripheral inner wall of the cyclone portion and a central axis and being connected as an outlet in the middle of the transfer pipe. And the fine particles belonging to the fine particle group A are kept in the cyclone portion and the circulating device without being put in the final collection container during the operation of the cyclone device. Step (4) Close the damper, weaken or stop the operation of the circulating device, weaken or stop the operation of the cyclone device, and drop and collect the fine particle group A. Collection process In the above step (1), the rotational speed or the peripheral speed of the impeller is increased or decreased, and / or the impeller interval between the two impellers is increased or decreased, thereby being represented by the following formula (1). 2. The fine particle group A-containing body according to claim 1, wherein the fine particle group A is produced by decreasing or increasing the epoxy resin content (CER [% by mass]).
CER [% by mass]
= 100 x [mass of epoxy resin in particle group (g) / [mass of particle group (g)] ... (1)   3. The fine particle group A-containing body according to claim 2, wherein the epoxy resin content (CER [% by mass]) of the fine particle group A is 0.5% by mass or more and 15% by mass or less.   The film is a film having a thickness of 40 μm or less, an electromagnetic wave shielding film, an electronic substrate shielding cover film, a conductive film, a film for preventing metal oxidation, a mulching film for agricultural use, a smoke film for a transparent member, or an antistatic film. The fine particle group A-containing substance according to any one of claims 1 to 3.   The fine particle group A-containing body according to any one of claims 1 to 3, wherein the nonwoven fabric is a heat-retaining nonwoven fabric for agriculture or a nonwoven fabric for a speaker.   The fine particle group A-containing body according to any one of claims 1 to 3, wherein the packing is a packing for stopping water from electric material, and the fiber is a fiber for an insect repellent net.   The fine particle group A-containing material according to any one of claims 1 to 3, wherein the electrode is a negative electrode for a fuel cell, a negative electrode for a lithium secondary battery, or a negative electrode for an electrolytic cell.   The fine particle group A-containing body according to any one of claims 1 to 3, wherein the paint is a conductive paint, an antistatic paint, or an antioxidant paint. A particle group B containing a particle group having a particle size distribution of 3 μm or more and 120 μm or less, a sheet, a coating material, a building material, furniture, and a particle group B-containing material selected from the group consisting of housings of electrical products,
The fine particle group B-containing material, wherein the fine particle group B is obtained by a production method having the following steps (1) and (2).
(1) Broad particles of the carbon fiber-containing epoxy resin are obtained by using an “air current crusher that has two or more impellers and crushes particles to be crushed by a swirling air current generated by rotation of the impellers to crush the particles.” Pulverizing step for obtaining a group (2) The transfer pipe, “a cyclone device comprising a cyclone part, a damper, and a final recovery container in this order from the airflow crusher side” are sucked, and the crushing step (1) is performed. ), While moving the broad particle group obtained in step (c) into the cyclone site, by operating the cyclone apparatus to collect fine particles belonging to “fine particle group B having a particle size distribution of 3 μm to 120 μm” in the final collection container. Group B recovery process In the above step (1), the rotational speed or the peripheral speed of the impeller is increased or decreased, and / or the impeller interval between the two impellers is increased or decreased to be represented by the following formula (1). The fine particle group B-containing material according to claim 9, wherein the fine particle group B is produced by decreasing or increasing an epoxy resin content (CER [% by mass]).
CER [% by mass]
= 100 x [mass of epoxy resin in particle group (g) / [mass of particle group (g)] ... (1)   The fine particle group B-containing body according to claim 10, wherein the epoxy resin content (CER [% by mass]) of the fine particle group B is 0.5% by mass or more and 15% by mass or less.   The sheet according to any one of claims 9 to 11, wherein the sheet is a conductive sheet, a heat conductive sheet, a snow melting sheet, a ground heating sheet, an anti-slip sheet, or an antistatic sheet having a thickness of 2000 µm or less. The fine particle group B-containing material according to the above.   The fine particle group B-containing material according to any one of claims 9 to 11, wherein the paint is a rust preventive paint, an anticorrosive paint, or a heat resistant paint. 12. The building material according to any one of claims 9 to 11, wherein the building material is a reinforced building material by forged composite (casting press method) or a lightweight and reinforced plate by extrusion molding, and the furniture is furniture with rails. The fine particle group B-containing body of the above.