JPH0457374B2 - - Google Patents

Description

Detailed Description of the Invention "Industrial Application Field" The present invention utilizes aggregation and coagulation reactions of aqueous colloid particles to produce regularly arranged packed particles, and after separating them from the aqueous particle colloid, the internal The present invention relates to a method for producing an aggregate of closely packed colloidal particles.

The aqueous particle colloid mentioned here is a particle that can be treated as a solid or gel with an aqueous phase as a dispersion medium, and the dispersed phase is 10 to 3000 Å in diameter.The aqueous particle colloid is a liquid in which the dispersed phase is charged and suspended in the aqueous phase. A liquid that can be coagulated and coagulated by adding a coagulant. Naturally, it also includes polymer latexes obtained by emulsion polymerization and the like.

"Prior Art and Problems" Conventionally, as a method for recovering colloidal particles from aqueous particle colloids, whether natural or artificial, since the colloidal particles are extremely minute, after forming aggregates of these particles, Usually, purification and drying processes are used. Although this type of technology is not limited to polymer latex, we will explain polymer (synthetic resin) latex, which is a typical aqueous colloid to which the present technology is difficult to apply due to its low softening temperature.

When recovering a resinous polymer, which is the dispersed phase, from a polymer latex, generally an aqueous solution of a coagulant such as an inorganic salt or an acid is added to the latex, or conversely, the latex is poured into an aqueous solution of a coagulant. It is solidified in a phase, made into a slurry through operations such as heat treatment, and then dehydrated and dried to obtain a powdered material. However, in the case of this method, the shape of the powder is amorphous, the powder particle size is difficult to adjust, the particle size distribution is wide, and a considerable amount of fine powder is included. the result,
Unfavorable results have occurred, such as loss due to scattering, frequent troubles in the process due to clogging with fine powder, deterioration of the working environment due to dust generation, and increased risk of explosion due to dust. In addition, because it is difficult to increase the bulk specific gravity of the powder, transportation costs, warehousing costs, etc. increase, and furthermore, dehydration, drying, fluidity, blocking resistance, etc. are poor, so expensive dehydration and drying equipment is required. was needed.

Extremely intense efforts have been made in the field of synthetic resin manufacturing to improve these problems. A method has been proposed in which spherical coagulated particles are recovered by absorbing the coagulated material into organic solvent droplets, removing the solvent, and solidifying the coagulated material. The background to the development of these various recovery methods is that the value of a product is increasingly determined by the quality of properties such as the distribution, size, and filling rate of the powder, rather than the physical properties of the polymer itself. There are trends of the times.

The former method has the disadvantages that it is difficult to use industrially for producing large particles of 500 μm or more or for producing highly heat-resistant polymers with a softening temperature of 80°C or more, and that it is difficult to tightly pack the inside of the particles. Yes, and in the latter method, removal of solvent, removal of impurities,
In addition to the difficulty of tightly packing the inside of particles, there are problems such as cost, quality, scope of application, particle characteristics, etc., such as the lack of organic solvents that can be used with this method depending on the type of polymer.

On the other hand, methods for obtaining solids by directly drying latex include spray drying and vacuum granulation drying, and many improvements have been made to the equipment. However, with these methods, it is difficult to remove contaminants from the latex, and in addition to requiring large-scale equipment changes when producing large particles, a large amount of thermal energy is required for producing latex at low concentrations. Therefore, there are significant constraints in terms of quality and cost, such as high processing costs. Furthermore, as a common problem in conventional methods, the quality problem of emulsion polymers remains unsolved because it is extremely difficult to remove impurities.

"Means for Solving the Problems" The present invention is a method developed for the purpose of solving the above-mentioned drawbacks all at once.

That is, the present invention provides (A) adding a coagulant to an aqueous particle colloid that causes a coagulation reaction by adding a coagulant at a temperature lower than the temperature at which colloidal particles fuse together (softening temperature); Before dissolving and diffusing into the colloid, coagulant units are dotted in the colloid dispersion, and (B) colloid particles are coagulated on the outer surface of the dotted coagulant units and stacked from the inside to the outside. (C) Separate the coagulated particles from the aqueous particle colloid to obtain coagulated particles; (D) At a temperature lower than the softening temperature of the colloidal particles. (E) By drying or heating in an aqueous phase while maintaining the temperature of the coagulated particles, coagulated particles in which colloidal particles constituting the coagulated particles are most closely packed are obtained, and (E) the coagulated particles are further heated to the softening temperature of the colloidal particles. The content is a method of heating and melting the above particles to obtain an aggregate of high-density colloidal particles having a dense and homogeneously packed internal structure with no voids inside the particles.

The present invention is applicable to all aqueous particle colloids in which a coagulation reaction is caused by the addition of a coagulant and the colloid particles can be recovered as a solid coagulation.

Here, solid means something that behaves as a solid or something that can be handled, and naturally rubber-like substances that are elastic bodies and gel-like plastic substances with high clay content are also included in the applicable range. Even if a solidified body exhibits fluidity at room temperature, it can be applied by operating under cooling if it becomes solid upon cooling. The present invention will be explained by taking polymer latex as an example of an aqueous particle colloid.

The present invention involves adding a coagulant into latex, suppressing the diffusion of the coagulant into the latex, and dispersing the coagulant into the latex to create scattered coagulant units. By coagulating and stacking latex particles on the outer surface, the coagulated particles grow from the inside to the outside around the coagulant unit, and then are separated from the latex as coagulated particles, and the softening temperature is reached after or without drying. This is a method of manufacturing particles by sintering at higher temperatures. The coagulated particles thus obtained are spherical particles in which the basic particles constituting the latex are regularly arranged in a crystal lattice.

The coagulant used in the present invention includes a substance that can coagulate latex, or a substance that produces a substance having a coagulation function through a reaction between a substance previously mixed in latex and a newly added substance.

The substance that can be solidified may be in a gaseous, liquid, or solid state. Alternatively, a coagulating slurry obtained by stirring and mixing latex and coagulant in advance may be used as the coagulant.

Further, as a reaction, a slurry pre-coagulated using the above-mentioned coagulant can be used as a coagulant for the same or different types of latex to produce a capsule-shaped composite. It is also possible to make a capsule-shaped composite by impregnating or mixing the coagulant into a powder prepared in advance and adding it to latex as a coagulant (this method is the same as preparing coagulation seeds in advance).

Coagulants used in liquid or solid state include, for example, sodium chloride, potassium chloride, lithium chloride, sodium bromide, potassium bromide, lithium bromide, potassium iodide, potassium sulfate, ammonium sulfate, sodium sulfate, ammonium chloride,
Sodium nitrate, potassium nitrate, calcium chloride, ferrous sulfate, magnesium sulfate, zinc sulfate,
Inorganic salts such as copper sulfate, barium chloride, ferrous chloride, magnesium chloride, ferric chloride, ferric sulfate, aluminum sulfate, potassium alum, iron alum, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid,
Salts of inorganic alkalis such as caustic soda, caustic potash, calcium hydroxide, and magnesium hydroxide; organic acids such as acetic acid and formic acid; and salts of organic acids such as sodium acetate, calcium acetate, sodium formate, and calcium formate, either singly or in mixtures. solid, liquid,
There are aqueous solutions and solutions in water-soluble organic solvents. The solid may be dispersed in a sparingly soluble and water-soluble organic solvent and added in the form of a slurry.

The latex that can be the object of the present invention may be anything as long as it is solid and consists of recyclable particles. For example, regarding polymer latex,
For example, it is as follows, and can be applied to almost all polymer latexes that can be recovered in resin form obtained by substantial emulsion polymerization or suspension polymerization.

The object may be a single or mixed latex of a polymer obtained by polymerizing, copolymerizing, or graft polymerizing a monomer composition mainly consisting of one or more monomers selected from the following monomer groups. However, it is natural to exclude those that cannot be polymerized. Vinyl aromatics such as styrene, monochlorostyrene, dichlorostyrene, α-methylstyrene; vinyl cyanides such as acrylonitrile, methacrylonitrile; acrylic esters such as methyl acrylate, ethyl acrylate, butyl acrylate; methyl methacrylate, ethyl methacrylate, butyl methacrylate Methacrylic esters such as; vinyl halides such as vinyl chloride, vinyl bromide, and vinyl fluoride; vinylidene halides such as vinylidene chloride and vinylidene bromide; acrylic acid, methacrylic acid, itaconic acid, maleic acid, vinyl acetate, ethylene, Propylene, butylene, butadiene, isoprene, chloroprene; crosslinking monomers such as allyl methacrylate, diallyl phthalate, triallyl cyanurate, monoethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, divinylbenzene, glycidyl methacrylate.

Further, in the present invention, the following polymer latexes can be particularly preferably used.

(1) A monomer consisting of 20 to 80 parts of acrylonitrile monomer, 20 to 80 parts of one or more mixtures of vinyl chloride, vinylidene chloride, vinyl bromide, and vinylidene bromide, and 0 to 10 parts of an easily dyeable monomer. A polymer latex obtained by polymerizing polymers.

(2) Styrene 0-5wt% (wt%, unless otherwise noted as % of other species, % is wt%), butadiene 50
A butadiene-based polymer latex consisting of ~100%.

(2′) Butadiene polymer latex of (2) 20 to 80
Acrylic esters 0-50%, methacrylic esters 0-10%, vinyl aromatics 0-90% in the presence of
%, vinyl cyanide 0-90%, and 0-20% monomer copolymerizable with 20-80 parts of a polymer latex.

(3) Styrene 0-50%, butadiene 50-100%,
In the presence of 0-20 parts of a rubbery polymer latex consisting of 0-30% of acrylic esters, 0-100% of methacrylate, 0-60% of other methacrylic esters or acrylic esters other than methyl methacrylate, 0-90% of vinyl aromatics. %, a polymer latex obtained by polymerizing 80 to 100 parts of a monomer consisting of 0 to 90% of vinyl cyanide.

(4) One type selected from vinyl aromatics, methacrylic esters, acrylic esters, and vinyl cyanides in the presence of 10 to 90 parts of a butadiene polymer consisting of 0 to 50% styrene and 50 to 100% butadiene. Or a graft copolymer (A) obtained by polymerizing 10 to 90 parts of two or more types of monomers, containing 0 to 50 parts and 0 to 70 mol% of α-methylstyrene, vinyl aromatic, methacrylic ester, acrylic ester. ,
30 to 100 mol% of one or more monomers selected from acrylic acid and vinyl cyanide
A mixed latex with 50 to 100 parts of a polymer (B) obtained by polymerizing monomers.

(5) 40 to 100% of acrylic ester and one or more monomers selected from vinyl aromatics, vinyl cyanide, vinyl chloride, vinylidene chloride, vinyl acetate, or conjugated diolefins.
60% and 0 to 10% of a crosslinking agent in the presence of 5 to 85 parts of a rubber polymer obtained by polymerizing methacrylic esters, vinyl cyanides, acrylic esters, vinyl aromatics, and copolymerizable therewith. One or more monomers selected from monomers
Polymer latex obtained by polymerizing 15 to 95 parts.

(6) 40 to 100 parts of vinylidene chloride and vinyl aromatic,
A polymer obtained by polymerizing 0 to 60 parts of one or more monomers selected from vinyl cyanide, acrylic ester, methacrylic ester, acrylic acid, methacrylic acid, itaconic acid, maleic acid, and crosslinking monomers. Molecular latex.

(7) 40 to 100 parts of vinyl chloride, 0 vinyl cyanide
~20 parts and one or more monomers selected from vinylidene chloride, vinyl bromide, vinylidene bromide, acrylic ester, methacrylic ester, acrylic acid, methacrylic acid, itaconic acid, maleic acid, and crosslinking monomers A polymer latex obtained by polymerizing 0 to 60 parts of the body.

In the first step of the present invention, a coagulant unit is prepared in which the coagulant is dispersed in the latex without being dissolved. As mentioned above, the coagulation reaction rate is generally extremely fast, so when the coagulant is dispersed and scattered in the latex as a unit, the coagulation reaction occurs in parallel, and a coagulated substance is formed around the outer periphery of the coagulant, covering its surface. Alternatively, the coagulated particles that have partially undergone the coagulation reaction may be divided and dispersed in the latex to form coagulated units. Therefore, in the coagulant unit, even if the coagulant is a liquid or gas, the scattered coagulation species actually have the coagulant in the center.
It can be considered that they are solid particles with a coagulated material around them.

Next, in the second stage, the latex particles coagulate and stack on the outer periphery of this coagulant unit, and the coagulated particles grow while renewing the outer surface. As long as the coagulation concentration on the outer surface of the coagulant unit is sufficiently high, all latex particles that collide with the coagulant unit will coagulate, but as the coagulated particles grow, the coagulant concentration on the outer surface decreases and they collide. Only a portion of the latex particles can solidify. The amount that can be solidified is determined by the amount of movement of the coagulant inside the coagulated particles, which is supplied to the surface through the coagulated and laminated latex particle layer. Since the movement of the coagulant from the inside to the surface is considered to be diffusion movement, it decreases as the coagulant concentration inside the coagulated particles decreases. In this way, the growth rate of coagulated particles, that is, the coagulation rate, slows down with time.

The key point in implementing the present invention is the first step. That is, in the first stage: (1) The slower the coagulation rate, the easier the coagulant will diffuse into the latex dispersion medium from the outer surface of the coagulated particles, and the coagulant concentration in the latex dispersion medium will increase. As a result, the latex coagulates and solidifies more easily.

(2) Furthermore, if the coagulated material layer formed on the outer surface is soft, the coagulated material will easily be redispersed into the latex, and the entire latex will similarly coagulate and become solidified.

Both (1) and (2) above are forms of conventional coagulation methods for creating an aqueous coagulation slurry.

Therefore, it is necessary to set conditions to prevent (1) and (2). If the coagulant is an aqueous solution and the concentration is dilute, both (1) and (2) are likely to occur, so a higher concentration is desirable. In addition, if it is dilute, it is difficult to form tight units of coagulant, so it is necessary to add a thickener to increase the viscosity or lower the temperature to suppress the dissolution and diffusion into the latex and the coagulation reaction until units are scattered. It is necessary to devise such measures. For the above reasons, it is easiest and most reliable to use a solid powder as a coagulant. Particularly when the coagulant is a liquid or gas, the higher the coagulation rate, the easier it is to obtain stable operation. In general, acids and polyvalent metal salts with a higher coordination number are easier to use, but conversely, if coagulation is too rapid, it becomes difficult to disperse coagulant units in the latex. Therefore, it may be necessary to control the concentration of the coagulant in the case of a liquid or by using air, nitrogen, or water-soluble carbon dioxide as a diluent in the case of a gas.

Furthermore, by controlling the temperature by cooling the coagulant and controlling the viscosity by adding a thickener, the relationship between the dispersion of the coagulant in the latex and the reaction rate and diffusion rate can be adjusted.

The same can be said about latex concentration. In other words, the more dilute the coagulate, the less frequently the reactant latex comes to the outer surface of the coagulated particles, and the coagulant tends to diffuse into the latex phase, which causes (1). As the solid content concentration decreases, the coagulated layer becomes softer, ie, (2) occurs. Therefore, the higher the latex concentration, the more reliably particles can be produced.

(1) If the coagulant is solid; place the latex in a beaker and stir.
Add a powdered solid coagulant such as salt, momentarily stir strongly so that it is dispersed in the latex, and then immediately stir gently. This state is maintained for 1 minute to 1 hour, stirring is stopped, and the latex is passed through a sieve mesh to remove coagulated particles. In this case, cool the beaker with ice water or the like as necessary. Furthermore, if the stirring is weak, the coagulant will settle to the bottom, resulting in hemispherical coagulated particles.

A powder dispersion of the coagulant is prepared in a water-soluble organic solvent such as alcohol or ketones that is insoluble or poorly soluble in the coagulant, and this is added to the latex.

(2) When the coagulant is liquid; Drop the coagulant into the latex.

Spray the coagulant into the latex and add fine droplets.

When adding the coagulant to the latex all at once, stir strongly only when adding the coagulant, and after the coagulant is dispersed dropwise into the latex, stir gently.

It is desirable to pre-cool the latex coagulant to reduce the stirring speed. No particular cooling is required after dispersion. Adding a thickener to the coagulant is also effective in suppressing diffusion and creating dispersed droplets.

(3) When the coagulant is a gas; Cool the coagulant gas and latex in advance, add it near the bottom of the stirring blade, and disperse the gas in the latex with strong stirring.

(4) When the coagulant is in the form of a slurry or solid impregnation: Usually, the same method as in the case of a solid is sufficient.

Note that the slurry form can be made by, for example, adding a diluted coagulant aqueous solution to latex while stirring it vigorously to form fine random aggregates to form a coagulated slurry. Further, solid-impregnated particles are particles containing a coagulant obtained by, for example, immersing powder particles in an aqueous coagulant solution, impregnating the particles with the coagulant, and then filtering the particles.

Further, the stirring during coagulation is set to a gentle strength that prevents the coagulation particles from colliding with each other after the coagulant units are scattered in the latex. However, if it is too weak, the coagulated particles will settle and come into contact with each other, resulting in coalescence. Since coagulated particles are constantly growing, they tend to coalesce. If the pressure is too strong, the coagulated particles will not only coalesce, but the coagulated particles will be destroyed, and the coagulant will be dissolved and diffused into the latex dispersion medium, making the entire latex more likely to coagulate. Particular care must be taken when the latex concentration is low or when a coagulant with weak coagulating power is used. For this reason, it is desirable that the liquid flow during solidification be in a laminar flow state.

As described above, setting the operating conditions during coagulation is a key point in embodying the present invention, so the absolute droplet distribution rate, coagulation reaction rate, diffusion rate of coagulant in coagulated particles, etc. Even if it is not possible to obtain exact values, it is necessary to understand the relative relationships in advance through experiments. To do this, it is important to know how the behavior of coagulated particle formation and the phenomena that occur in latex qualitatively change in response to changes in operating conditions such as temperature, viscosity, and stirring speed as described above. is required.

Further, in the present invention, the coagulated particles must be separated from the coagulation system in a state where the latex particles are not fused together. Therefore, the coagulation operation must be performed while the temperature of the coagulation system, that is, the entire latex bath, is maintained at a low temperature below the softening temperature of the latex particles. Therefore, in the case of a polymer latex whose softening temperature is lower than the latex temperature, it is necessary to carry out this solidification operation under cooling.

In the center of the coagulated particles obtained in this manner, a slight random coarse filling part is observed. The size of this random rough filling part tends to be larger as the coagulant has a faster coagulation rate, and when the coagulant is a liquid, the smaller the concentration is, the larger it is. Furthermore, if the coagulant is solid, a void remains in the center of the particle, indicating the presence of the solid. In any case, since such coarsely packed parts and voids in the center of the particle are extremely small compared to the entire particle, it can be regarded as a homogeneous packing as a whole.

"Operation/Effect" Although the present invention does not appear to be different in terms of operation at first glance compared to conventional coagulation methods, it is fundamentally different. The essential difference is that the coagulum particles in conventional methods are randomly arranged aggregates of latex particles. Conventional methods can be broadly classified into three types, and will be explained based on these three types of operations.

(1) The first method is to mix latex with a coagulant and coagulate it. Usually, an aqueous solution of acids or salts is used as the coagulant, and the coagulant is mixed and diffused into the latex. In this case, three phenomena occur simultaneously in the coagulation system: mixing of the coagulant and latex, diffusion of the coagulant into the latex dispersion medium, and coagulation of the latex particles. In general, since the coagulation reaction rate is extremely fast, the phenomenon is that a coagulated lump is generated at the contact area between the latex and the coagulant, the coagulated lump is crushed and divided by external force such as stirring, and unreacted during the crushing and dividing process. A step is observed in which the whole latex is mixed with latex and divided while solidifying. Therefore, the coagulated particles are obtained in the form of a nearly homogeneous slurry dispersed in the aqueous phase, and there is no need to separate the coagulated particles from the latex as in the present invention.

The random aggregates obtained in this way contain a large amount of water and exhibit thixotropic fluidity, and do not exhibit liquid-like behavior even if the solid content concentration in the slurry is reduced to a low concentration of 20% or less.
Adjustments such as adding water to dilute are required during coagulation. When the solid content concentration is extremely low, only a small stirring force is required, and in some cases, a solidified slurry can be obtained using only a water stream.

Furthermore, if a dilute coagulant aqueous solution with weak coagulating power is used to make the coagulation reaction lower than the dissolution/diffusion rate, the coagulant concentration in the latex dispersion medium becomes high and the entire latex coagulates at the same time. Without stirring, a solidified latex body similar to agar is formed, and under stirring, an aqueous slurry containing fine particles dispersed close to individual latex particles is formed.

(2) Next, there is a method of adding the latex to the aqueous coagulant solution in the form of dispersed droplets or as a streak or band-like fluid using a nozzle or the like.

This method is based on the idea of creating particles by causing a coagulation reaction in the form of dispersed latex droplets, or in the case of streaks or bands, in the form of particles separated in a coagulant. At this time, the degree of fragmentation determines the particle size, so the flow strength and temperature of the coagulating liquid must be controlled, but since the latex particles are easily dispersed in the aqueous phase and the coagulating particle retention force is extremely small. Efforts are taken, such as raising the temperature above the softening temperature of the latex particles to fuse the surface layer of the coagulated particles to increase the holding power. Therefore, since the coagulation reaction and fusion of the latex particles proceed rapidly and simultaneously, a coagulated body in which the inside of the particles is randomly and loosely filled cannot but be formed.

The coagulated particles obtained in (1) and (2) above are, of course, amorphous particles with a wide flow distribution.

(3) Furthermore, there is a method of spraying latex droplets into the gas phase of a coagulating atmosphere to obtain spherical coagulated particles.

This method eliminates the drawback of (2) and is an excellent method in that it uses surface tension to create a spherical shape, but it has limitations in the following two points.

(a) Similar to (2) above, this is a problem that occurs when the latex liquid mass is coagulated from the outside, and the coagulated particles do not shrink and the excess water that remains inside prevents them from being arranged in an orderly manner, leaving voids inside after drying. arise.

(b) When particles are collected by falling from the gas phase, fine powder is more likely to be generated under conditions that reduce the number of voids inside the particles (for example, low temperature). Furthermore, the equipment becomes larger and it becomes difficult to produce large particles.

In the conventional method as described above, even if the recovered coagulated particles are dried and sintered, it cannot be expected that the inside of the particles will be filled into a homogeneous continuous layer. The reason for this is presumed to be that the latex particles constituting the particles are randomly arranged and coarsely packed. The voids herein refer to voids or cavities larger than the latex particles, and do not mean voids smaller than the latex particles that occur when the latex particles are packed closest to each other without being fused. In this way, in all conventional methods (1), (2), and (3), the coagulated particles are separated from the aqueous phase, whereas in the present invention, they are separated from the latex. This suggests a fundamental difference between the two.

On the other hand, the method of the present invention first creates a state in which a high concentration of coagulant is scattered in the latex without dissolving the coagulant in the latex dispersion medium, and creates coagulated particles in which latex particles are layered around them.
Since the coagulant is then allowed to naturally diffuse from the inside of the particle to the surface, the coagulation reaction becomes a system dominated by the diffusion movement of the coagulant. It is thought that by doing so, the unit particles are regularly arranged in the coagulated body. In addition, when latex particles grow as a coagulate, the latex particles tend to form a close-packed arrangement with a low energy level.
The particle density of the coagulum is greater than that of the latex. The degree of density depends on the coalescence strength of the unit particles and the degree of time allowance for arrangement. That is, when latex particles come into contact with each other through a coagulation reaction, if the strength of the fusion bond is large, the latex particles cannot be densely arranged. This is determined by the balance between the softening temperature of the latex particles and the temperature of the coagulation system. However, since the attractive force between latex particles is only Van der Waals force, which is a small force, the degree of dense arrangement is not large even if the coalescence strength is small. To increase this level, it is necessary to apply an external force, and specifically, there is a means to control the flow state and create a vortex. However, in this case, there is a limit to the size of the particles. On the other hand, the slower the coagulation reaction rate and the slower the diffusion rate of the coagulant, the more time there is for alignment of the latex particles, so the degree of filling increases. When latex particles are not fused at all, the only bonding force between the particles is the small Van der Waals force, but by forming a network with multiple particles, the coagulated particles have a strong holding force that makes them difficult to break. Become. This is because as the number of latex particles in contact with each other increases,
In other words, as the filling rate within the coagulated particles increases, the bonding of the latex particles becomes more regular, and the number of adjacent particles naturally increases, so the holding force increases. Moreover, it can be sufficiently handled industrially as a solid even without fusion. The required strength depends on the handling of the coagulated particles, but as mentioned above, it also depends on the physical properties of the latex particles and the filling rate of the latex particles in the coagulated body.
Generally speaking, the filling rate is 10vol when expressed as solid content concentration.
% or more, preferably 20vol% or more, and the larger the better. Therefore, if there are restrictions on the hardness or strength of the coagulated material, it is necessary to take measures such as pre-concentrating the latex to be coagulated or slowing down the coagulation reaction rate and diffusion rate. Since the coagulated particles with such a high filling rate have a high retention strength, they can avoid deformation and destruction when subjected to physical operations such as separation and washing from the latex. The regularity of the packing of latex particles in the solidified particles obtained in this way is explained by the fact that regular step-like layered cleavage planes are observed on the cut surface of the solidified particles. This can be confirmed because it can be assumed that the

In the conventional method, in order to treat the coagulated material as solid particles, the holding strength must be increased and the latex particles must be fused together, so it is necessary to solidify at high temperatures, heat treatment, etc. For heat-resistant resins with a high softening temperature, it was necessary to add an organic solvent such as toluene or a binder to promote fusion bonding, but these are completely unnecessary in the present invention.

The size and flow rate distribution of the coagulated particles in the present invention depend on the size and distribution of each unit of coagulant dispersed in the latex, as well as the coagulation time and its dispersion. Essentially, the present invention is a method suitable for producing particles of uniform particle size without worrying about the generation of fine powder. If it is desired to form fine particles, it is sufficient to disperse a coagulant with a small coagulating power into the latex in small units and separate it in a short period of time. On the other hand, large particles can be created by simply doing the opposite, and the size can be controlled freely. Generally suitable for obtaining particles with a diameter of 200 μm to 1 cm. On the other hand, it is easy to obtain a uniform particle size distribution, but if you want to further improve the uniformity, it is necessary to make the coagulant units dispersed in the latex the same size and to make the coagulation time the same. Desirably, especially in the case of continuous operation, it is necessary to take measures to make the residence time of the coagulated particles the same in the coagulation device.

Regarding particle size, there is coalescence of coagulated particles. In the coagulated particles created by the present invention, the latex particles are regularly arranged and form a solid unit, so when growth is stopped, they will not coalesce even if they come into contact in the latex. . There is no fear of coalescence as long as the temperature is kept below the softening and melting temperature of the latex particles. However, when the coagulated particles are growing by coagulating surrounding latex particles, they tend to coalesce and coalesce, especially in the initial stage of coagulation. In order to prevent the formation of coalesced particles, it is necessary to take measures such as reducing the density of the coagulated particles in the latex or applying kinetic energy to the coagulated particles by stirring or the like. Care must be taken that extremely strong agitation can break up the coagulated particles and cause the entire latex to coagulate and solidify. A slow laminar flow is desirable for the growth of coagulated particles.

In this way, the size of the coagulated particles can be freely determined from fine to lumpy, but the final size of the dried particles and sintered particles must be determined without considering the degree of shrinkage due to the amount of water contained in the coagulated particles. It won't happen.

Regarding the creation of such coagulated particles, if the physical properties of the latex particles to be treated are known, it is possible to select the range of operating factors such as coagulant type, properties, stirring conditions, temperature, residence time, etc., but the exact number depends on experimentation. In reality, it is important to have a clear qualitative understanding of the mechanism of coagulated particle generation mentioned above, and to know the behavior of how coagulated particles change in response to changes in operating factors. It is sufficient. When carrying out the present invention, the biggest concern is that the coagulant that should be dispersed and dotted will partially dissolve and diffuse into the latex dispersion medium, impeding the stability of the entire latex and eventually causing the entire latex to coagulate. This means falling into the so-called conventional coagulation format. In normal operations, this can be easily confirmed by selecting the conditions such as the latex concentration, type of coagulant, form, concentration, temperature, and stirring described above. however,
If the process is difficult due to significant constraints in terms of quality and cost, it may be necessary to stabilize the latex or improve the equipment. For example, to stabilize latex, it is possible to add or add latex stabilizers such as dispersants and emulsifiers, or to coagulate while adding them. In order to suppress dissolution and diffusion into the existing latex dispersion medium, a coagulant is dropped into an atmosphere containing atomized latex to create a coagulated species whose outer periphery is covered with coagulated material, which is then recovered and dispersed in the latex. It is also possible to cause growth by coagulation.

The coagulated particles obtained in this way have latex particles arranged with considerable regularity, so
Further compaction is easily achieved by simply removing water.

When the coagulated particles are dried at a low temperature that prevents fusion of the latex particles, capillary forces are generated and the latex particles are attracted to each other and rearranged densely to form a nearly perfect hexagonal close-packed body. This means that it is not possible to obtain free cut planes when dividing this dry body, and the appearance of cleavage planes suggests that it has a crystalline structure. It is inferred from the fact that they all have the same monoclinic or hexagonal crystal shape, and that the filling rate of the latex particles is 73% or more. In this way, when drying is carried out at a temperature that does not allow the fusion of latex particles, even though the particles are tightly packed, the gaps between the latex particle tubes are continuously connected, making it extremely easy for volatile substances to collect. will be removed. This not only removes impurities, but also facilitates the drying and removal of water present inside the particles, that is, in the spaces between the latex particles.

Particle shrinkage due to close packing of latex particles also occurs when the latex particles are immersed in an aqueous phase at a high temperature to the extent that they do not fuse and coalesce.

As described above, heat treatment narrows the gaps between latex particles in the coagulated particles, thereby greatly reducing the water content, and is therefore an effective means of energy saving when energy consumption during drying is an issue. In addition, the content of intragranular impurities due to discharge of internal water due to contraction of coagulated particles and diffusion into the aqueous phase can also be effectively reduced. At the same time, water-soluble impurities can be easily extracted and reactions with acids and alkalis can be easily carried out through the gaps between the latex particles. Furthermore, when heat-treated in the aqueous phase at a temperature above the softening point, the surface layer first becomes a continuous layer, so internal water cannot be discharged and voids remain within the grains even after drying. The extent of this is determined by the balance between the fusion of the surface layer and the rate of water dissipation; the higher the temperature, the faster the fusion progresses and the larger the voids become.

When the coagulated particles thus obtained are dried while being kept below their softening temperature, capillary force is generated as the water existing between the latex particles within the coagulated particles is removed, and a strong force forces the latex particles together. A pulling effect appears, causing the coagulated particles to shrink and the filling rate to increase. In the drying process, if you want to create a loosely packed part inside the particles, you can increase the balance between the dissipation rate of water inside the particles and the fusion rate of the latex particle tubes, and drying at high temperatures is sufficient. Good. Once the latex particle tubes are fused, they can no longer be rearranged and become dry particles with voids still included. The softening temperature here means the temperature at which the substances fuse together under atmospheric pressure, and can generally be considered as the melting point of the substance. However, it is difficult to define a polymer because there is no clear melting point, and even if the polymer is the same, it is determined not only by the degree of polymerization and its distribution, but also by the crystallinity and impurities that give a plasticizing effect. to be influenced. However, in reality, if the glass transition point is Tg (°C), it can be considered to be in the range of Tg+273/0.8-273 to Tg+273/0.6-273 (°C). When implementing the present invention specifically, if the approximate value of Tg of the polymer is known, the approximate value of the softening point can also be determined, so it is easy to find the optimum temperature range by trying 2 to 3 temperatures. I can do it.

The validity of the above equation was confirmed by using a scanning electron microscope to observe the presence or absence of fusion of latex particles using a scanning electron microscope, using polymer latexes with different softening temperatures and operating them at various temperatures. Confirmed by. When particles that have shrunk and become densified through drying or heat treatment are cut into pieces, inside the particles there are striped patterns that indicate traces of growth and a regular step-like layered arrangement of crystal planes. will also appear more clearly. Considering this in conjunction with the cleavage plane, particle contraction occurs along the crystal plane.

After drying the solidified particles in this manner, by sintering them at a high temperature higher than the softening temperature at which the unit particles melt and fuse with each other, it is possible to obtain filled particles with no voids inside the particles. This treatment renders the particles homogeneous and molten inside, resulting in further shrinkage. As a result, the particles come to exhibit a transparent and glossy appearance, and resinous particles become transparent particles. Since this sintering operation can be carried out simultaneously with the drying operation, that is, continuously, the sintering operation can be carried out with the solidified particles as they are or immediately after the heat treatment. However, if the surface layer of the particles fuses and becomes a continuous layer with water remaining inside the particles, voids will be created inside the particles, so it goes without saying that consideration must be taken, such as keeping the temperature conditions low. . In addition, if there is a concern that the material may oxidize due to performing this sintering operation in air, it may be treated in an oxygen-free atmosphere, for example, in an inert gas such as nitrogen, in superheated steam, or in a vacuum. . The higher the temperature at which the sintering operation is performed, the faster the operation can be completed as long as quality deterioration due to polymer decomposition, oxidation, etc. does not occur. In addition, by combining temperature and operation time, the degree of fusion and dissolution of latex particles inside the particles can be easily controlled.
It is possible to adjust and obtain the desired state according to the purpose.

In order to achieve internal packing through such a sintering process, it is considered important that the latex particles in the dry particles serving as the raw material are regularly and most closely packed. Even if the particles obtained through the sintering process form a homogeneous continuous layer with a molten interior, cleavage planes appear when the particles are cut. In other words, cutting is more likely to occur in certain aspects,
In other respects it is extremely difficult. In addition, a step-like layered crystal structure appears more clearly than in the particles before sintering, and the striped pattern, which is thought to be the growth surface, becomes clearer.

If there are voids inside the particles, such as particles formed by conventional methods in which latex particles are randomly bonded, the sintering process will only cause the latex particles to simply fuse and coalesce, and no rearrangement will occur. Therefore, voids cannot be eliminated. This is regardless of the sintering temperature. Since it is not possible to remove the inter-particle voids in the particles produced by such conventional methods, it is necessary to first degas the melt through an extruder to form pellet-like particles. in this way,
It requires a large amount of energy at a much higher temperature and pressure than the sintering temperature.

In the particles obtained according to the present invention, a small amount of random coarsely packed portions formed in the center of the solidified particles at the initial stage of solidification do not sufficiently shrink and remain as voids, as described above, regardless of whether before or after sintering. This is the same phenomenon as in the conventional method where coagulated particles do not shrink sufficiently. Similarly, when the coagulant is solid, the microcavity at the center remains without sufficient contraction. However, these microscopic voids in the center are extremely small compared to the entire particle, and the entire particle can be considered to be a densely packed body.

The particles thus obtained have the following characteristics; (1) Volatile organic solvents, including salts, organic water-soluble impurities, oil-soluble impurities, and residual monomers can be easily removed. . In other words, it can be recovered as highly pure particles.

Until the sintering operation, the interstices between the latex particles in the particles remain unblocked and continuously connected, making it easy to penetrate or wash in water or solutions such as acid-alkali, or even organic solvents such as alcohol or ketones. It is easy to extract water-soluble impurities and oil-soluble impurities from work and remove them by washing. or,
In a drying operation or a stripping operation using aeration or the like in an aqueous phase dispersion, volatile components can be removed extremely quickly, making it easy to remove high-boiling volatile substances. In this way, the particles obtained according to the present invention can be of extremely high purity.

On the other hand, since it is necessary to increase the particle retention strength of particles obtained by conventional methods, the latex particles are fused by heat treatment or addition of an organic solvent. As a result, the surface layer of the particle becomes a continuous polymer layer, so that in order for intragranular substances to move to the outside of the particle, they must diffuse through the continuous polymer layer, and the movement speed becomes extremely low. For this reason, it has become industrially difficult to remove contaminants from particles obtained by conventional methods. This is also the reason why emulsion polymerization is considered a drawback.

(2) Easily dispersed and dissolved in solvents.

In applications where once dried particles are dispersed or dissolved in an aqueous solution or an organic solvent, the dispersion rate and dissolution rate are fast, and even latex particles can be finely dispersed.

Normally, when dissolving a polymer in an organic solvent, a method is used in which the dissolving power of the solvent is lowered, such as by lowering the temperature, and the particles are first uniformly dispersed in the solvent, and then the particles are dissolved by raising the temperature. With the particles of the present invention, the latex particles are not fused together by the solvent penetrating the gaps between the latex particles, so the latex particles can be easily dispersed into the solvent separately. As mentioned above, since it is a fused body, the dispersion unit is the particle itself, so the dispersion and dissolution operations are extremely slow. Therefore, in the conventional method, it is necessary to produce fine powder at the expense of the powder properties, which causes various problems in production.

(3) The particles have excellent physical properties and characteristics.

The particles obtained by the sintering process become dense and heavy particles, as they become filled to the same degree as pellets or molded products, which are melts obtained through a processing molding machine.

The granules obtained in this way do not generate any fine powder and are uniform in particle size, so they not only flow well and are convenient to handle, but also, in the case of polymers, can be used for extrusion molding, injection molding, etc. It is possible to improve productivity during processing and molding, improve workability during compounding and blending, significantly improve the environment against dust, and automate processing. In addition, since it is a high-density powder, it not only reduces packaging and transportation costs, but also greatly improves blocking and bridging in storage tanks, allowing it to be transported by truck, in bulk, and stored in silos. . In addition, it completely eliminates the drawbacks of conventional emulsion polymers, which required a pelletizing process due to the deterioration of the surface condition of injection molded products due to the amount of voids within the particles and impurities, and made direct injection molding possible. It has many features and can be expected to have many benefits such as energy saving, labor saving, and cost saving.

According to the present invention, not only can dry particles that are close-packed particles and sintered particles that are densely packed unit particles as described above be obtained, but also the interior of the particles can be It is possible to freely design the structure; that is, the degree of filling and filling form within the particles can be adjusted by balancing the rate of water discharge to the outside of the particles during aqueous phase heat treatment or drying and the rate of fusion of latex particles. do.

During sintering, the melting degree of latex particles is adjusted to change the packing density.

"Examples" The present invention will be described below with reference to Examples and Comparative Examples, but the present invention is not limited in any way by these.

Example 1 A polymer latex prepared by graft copolymerizing a mixture of styrene, acrylonitrile and methyl methacrylate onto a butadiene polymer, the polymer latex consisting of 60% butadiene, 10% methyl methacrylate, 10% acrylonitrile and 20% styrene. (A) 35% and α-methylstyrene 20
%, a homocopolymer polymer latex (B) consisting of 25% acrylonitrile and 55% styrene, 67% of which is mixed, the solid content concentration in the latex is 30%, and the temperature is 30°C. Take 300ml of in a 500ml beaker, d/D=
Stirring was carried out at room temperature at 400 rpm using a 0.5 raking three-propeller blade. Granular salt as a coagulant (particle size
0.2 to 0.5 mm) was added thereto and dispersed, and after about 10 seconds, the rotation speed was increased to 10 rpm, and the treatment was performed for 20 minutes with gentle stirring.

Next, the coagulated particles were separated from the polymer latex through a 60-mesh sieve, washed with water, dehydrated using a Nutsuie, and then dried at 70° C. for about 4 hours using a box dryer. Furthermore, at 140℃ in a nitrogen atmosphere
After 30 minutes of sintering, the result was a pearl-like luster and transparency with a bulk specific gravity of 0.66 (g/cm ³ ) and a particle size distribution of 6 to 6.
A highly sharpened and highly packed pearl-like powder with a mesh size of 98% was obtained. Note that no fine coagulated particles were mixed in the separated latex.

Comparative Example 1 When the same operation as in Example 1 was carried out at the initial setting of 400 rpm without lowering the rotation speed after adding the coagulant, the entire coagulation started after about 15 minutes, and after 18 minutes, All the latex in the beaker coagulated and solidified, and it was not possible to form particles.

Example 2 A polymer latex made by graft copolymerizing a mixture of styrene and methyl methacrylate onto a copolymer of styrene and butadiene, consisting of 35% styrene, 30% methyl methacrylate, and 35% butadiene, with a solid content concentration of Pour 300 ml of 30% polymer latex into a 500 ml beaker, cool it externally to 5°C with ice water, and stir gently at 100 rpm using a 3-bladed propeller blade with d/D = 0.5.
Concentrated hydrochloric acid solution cooled to 5°C (approx.
%) was added dropwise with a pipette.

After processing for about 10 minutes, the coagulated particles were dispersed from the polymer latex using a 60-mesh sieve, and the polymer latex was dehydrated using a water rinsing nuttie, followed by drying at 40° C. for about 5 hours using a box dryer. Furthermore, at 120℃ in a nitrogen atmosphere
When the particles were sintered for 40 minutes, the obtained particles had almost no intragranular voids, were highly packed, had a pearl-like luster, and had a bulk specific gravity of 0.55 (g/cm ³ ).

Comparative Example 2 When the same operation as in Example 2 was carried out with the coagulant concentration being 1%, all of the latex in the beaker coagulated and solidified several seconds after the coagulant was added, and no particles could be formed.

Example 3 A polymer latex copolymerized with a mixture of acrylonitrile and vinyl chloride, consisting of 50% acrylonitrile and 50% vinyl chloride, with a solid content concentration of 25.
% polymer latex at 15℃ in a 500ml beaker.
Take 300ml, put it at room temperature, stir it strongly at 400rpm through 3 propeller blades with d/D≒0.5, add calcium chloride powder as a coagulant and disperse it, and after about 10 seconds reduce the rotation speed. The temperature was set to 10 rpm, and the treatment was performed for 10 minutes with gentle stirring.

The coagulated particles were then separated from the polymer latex using a 60-mesh sieve, washed with water, dehydrated using a Nuttsuie, and then dried at 50° C. for about 5 hours using a box dryer. Furthermore, when a sintering process was performed at 100°C for 30 minutes in a nitrogen atmosphere, a powder with highly sharp transparency and high density was obtained. The bulk specific gravity is
It was 0.68 (g/cm ³ ).

Comparative Example 3 In Example 3, the same operation was carried out with the solid content concentration of the polymer latex being 3%, and when it was separated after 2 minutes, coagulated particles were formed, but they were soft and had extremely poor holding power, so a sieve was used. When separating the polymer latex and coagulated particles, the particles were broken. However, after about 5 minutes, the entire latex began to solidify and turned into a viscous agar-like solid.

Example 4 A polymer latex copolymerized with a mixture of α-methylstyrene and acrylonitrile.
300 ml of polymer latex made of 70% methylstyrene and 30% acrylonitrile with a solids content of 35% at 15°C was placed in a 500 ml beaker and stirred vigorously at 400 rpm using a 3-bladed propeller blade with d/D≒0.5. Add a slurry of aluminum sulfate powder dispersed in acetone as a coagulant with a pipette, disperse it into the latex, and after about 10 seconds, reduce the rotation speed.
The temperature was set to 100 rpm, and the treatment was carried out for 10 minutes with gentle stirring.

The coagulated particles were then separated from the polymer latex using a 60-mesh sieve, washed with water, dehydrated using a nutsie, and then dried at 100° C. for 3 hours in a box dryer. Further heat treatment at 150℃ for 30 minutes in a nitrogen atmosphere resulted in a transparent bulk specific gravity of 0.70.
(g/cm ³ ), 6-16 mesh, highly packed and highly sharpened powder of 98%.

Comparative Example 4 In Example 4, the initial rotation speed was 100 rpm,
When similar operations were carried out, the obtained coagulated particles were mostly lump-shaped and coalesced, and in addition to having poor fluidity, the bulk specific gravity decreased to 0.6 (g/cm ³ ). Adhesion of coagulum was observed on the feathers.

Example 5 A latex made by graft copolymerizing a mixture of styrene and acrylonitrile onto a butadiene copolymer, comprising 65% butadiene and 10% acrylonitrile.
% and 25% styrene.
A polymer latex obtained by mixing 30% (A) with 70% (B), a homocopolymer polymer latex consisting of 70% α-methylstyrene, 10% methyl methacrylate, and 20% acrylonitrile. 300 ml of polymer latex with a concentration of 30% and a temperature of 30°C was placed in a 500ml beaker, cooled to 2°C with ice water, and stirred vigorously at 400 rpm using 3 scraping propeller blades with d/D≒0.5 to solidify. Add and disperse a 30% calcium chloride aqueous solution cooled to 0°C as an agent, and after about 1 second, increase the rotation speed to 100 rpm.
The mixture was treated for 10 minutes with gentle stirring.

Next, the coagulated particles were separated from the polymer latex using a 60-mesh sieve, washed with water, dehydrated using a Nuttsuie, and then dried at 95° C. for 3 hours in a box dryer. Furthermore, when sintering was performed at 140°C for 30 minutes in a nitrogen atmosphere, densely packed granules with almost no intragranular voids were obtained. The obtained granules had a bulk specific gravity of 0.65 (g/cm ³ ), had a true spherical luster, and were highly transparent particles.

Example 6 A copolymer latex in which a mixture of styrene and methyl methacrylate was graft-polymerized onto polybutadiene, consisting of 40% styrene, 15% methyl methacrylate, and 45% butadiene, with a solid content of 25% and a polymer temperature of 15°C. Pour 300ml of latex into a 500ml beaker and fry it at room temperature with d/D≒0.53
The mixture was strongly stirred at 400 rpm using a propeller blade, and magnesium sulfate powder was added and dispersed as a coagulant. After about 10 seconds, the rotation speed was increased to 100 rpm, and the mixture was treated for 10 minutes with gentle stirring.

The coagulated particles were then separated from the polymer latex using a 60-mesh sieve, washed with water, dehydrated using a Nutssie, and then dried at 35° C. for 6 hours in a box dryer. Further, when sintering was performed at 120° C. for 40 minutes in a nitrogen atmosphere, a densely packed powder with almost no intragranular voids and a bulk specific gravity of 0.47 (g/cm ³ ) was obtained.

Example 7 A polymer latex prepared by graft copolymerizing a mixture of methyl methacrylate and styrene onto a butadiene polymer, comprising 33 parts of a polymer latex consisting of 75% butadiene, 20% methyl methacrylate, and 5% styrene, and α - 45% methyl styrene and 5% methyl methacrylate, 35% styrene
% and 67 parts of a homocopolymer latex consisting of 15% acrylonitrile, which is a polymer latex at 15°C with a solid content concentration of 30%, was placed in a 500 ml beaker, and 300 ml of the polymer latex was mixed, and
As a preliminary preparation, 2 ml of the above latex was separately placed in a 50 ml beaker, 4 ml of a 15% aqueous calcium chloride solution was added to solidify it, and the mixture was ground with a spatula to form a finely divided solidified slurry. into a 500ml beaker
While stirring the polymer latex in 300 ml at room temperature using three propeller blades with d/D≒0.5 at 400 rpm, the solidified slurry was added and dispersed, and after 10 seconds. , rotation speed
The treatment was performed for 10 minutes with gentle stirring at 100 rpm.

Next, coagulated particles were separated from the polymer latex using a 60 mesh sieve, washed with water, dehydrated, and dried at 100° C. for about 3 hours using a box dryer. Furthermore, when a sintering treatment was performed at 140° C. for 30 minutes in a nitrogen atmosphere, the obtained particles were highly packed with almost no intragranular voids. Bulk specific gravity 0.64
(g/cm ³ ), highly transparent particles with pearl-like luster were obtained.

Example 8 A polymer latex which is a copolymer of styrene and butadiene, consisting of 30% styrene and 70% butadiene, cooled to 0°C with a solid content concentration of 25%, was
Pour 100ml into a ml beaker and add 0 as a coagulant to this.
Add several drops of concentrated hydrochloric acid cooled to ℃ with a pipette,
The treatment was carried out for 10 minutes while stirring by gently shaking the beaker by hand.

Thereafter, coagulated particles were separated from the polymer latex using a 60-mesh sieve, washed with water, dehydrated using a Nutssie, and then vacuum dried at room temperature to obtain transparent elastic particles.

Example 9 A polymer latex prepared by graft copolymerizing a mixture of acrylonitrile, methyl methacrylate, butyl acrylate and styrene onto a copolymer of styrene and butadiene, comprising 4% acrylonitrile, 40% methyl methacrylate, and styrene.
300 ml of a polymer latex with a solid content of 8%, consisting of 40% butyl acrylate, 3% butadiene, and 13% butadiene, was placed in a 500 ml beaker, and d/
30 ml of a 0.5% HCI aqueous solution was added to a 3-blade propeller blade of D≒0.5 while stirring at 500 rpm.
The whole thing instantly turned into a viscous solidified slurry.

While continuing to stir, the mixture was heated to 75°C using an electric heater. After being transferred to a large amount of water and cooled, it was dehydrated using a Nutsuchie, and irregularly shaped particles were collected.

This dehydrated resin was dispersed and immersed in a large amount of 30% CaCl ₂ aqueous solution for 1 hour, and then dehydrated again using a Nuttsuie. The obtained resin was a water-containing resin containing CaCl, and was used as a coagulant.

Pour 300 ml of 35% solids polymer latex made by emulsion polymerization of only vinyl chloride into a 500 ml beaker.
The above resin was added little by little with a spatula while stirring at 400 rpm at room temperature using the above stirrer. Immediately the stirring was reduced to 100 rpm and left as it was for 20 minutes. When the coagulated particles were separated from the latex using a 60 mesh sieve, smooth oval spherical coagulated particles were obtained. The coagulated particles were dried in a box dryer at 50°C and then sintered at 120°C for 30 minutes in a nitrogen atmosphere. The obtained particles were composite particles with a capsule-shaped interior containing the polymer used as a coagulation seed and an exterior PVC layer. These particles had a pearl-like luster, were transparent, had a bulk specific gravity of 0.59 (g/cm ³ ), and were densely packed inside.

Example 10 A polymer latex copolymerized with a mixture of α-methylstyrene and acrylonitrile,
- 500% polymer latex made of 70% methylstyrene and 30% acrylonitrile with a solids concentration of 35%
300ml was placed in a ml beaker and cooled to below 5°C with ice water. Three d/D scraping propeller blades were placed in the latex, and a glass tube with a constricted tip was placed close to the lower end of the propeller blade to serve as a coagulable gas supply pipe.

Once HCI gas is released from the cylinder as a solidifying gas,
HCI gas cooled to below -5°C is passed through a glass tube through a gas retainer cooled to -20°C at 600 rpm.
The mixture was fed into the latex while being stirred. Once the HCI gas supply was stopped, the speed was immediately reduced to 100 rpm and kept under gentle stirring for 10 min.

Coagulated particles were separated from the polymer latex using a 60 mesh sieve, washed with water, dried in a box dryer at 105℃ for 2 hours, and then dried at 140℃ for 30 minutes in a nitrogen atmosphere.
Separate sintering treatment was performed. Bulk specific gravity of transparency 0.69 (g/
cm ³ ) highly packed particles were obtained.

Example 11 300 ml of polystyrene latex with a solid content concentration of 14% obtained by polymerizing only styrene monomer using ammonium persulfate as a polymerization initiator without an emulsifier was placed in a 500 ml beaker, and a 3-blade propeller with d/D = 0.5 was placed. Stirred to room temperature using a blade at 400 rpm. Ten grains each of 0.8 mm in diameter of common salt, calcium chloride (anhydrous salt), and aluminum chloride (hexahydrate) were added. One minute after addition, the rotation speed was increased to 100 rpm, and stirring was continued for 30 minutes.
It was separated from the latex using a 60 mesh sieve and washed with water. The number of particles was 10, the same as the number of salt particles, and all were almost perfectly spherical. After drying these particles at 50℃ for 3 hours, they were further dried at 140℃ in a dryer.
Heat at ℃ for 30 minutes. The obtained particles are almost transparent beads, with an average diameter and average weight of 3.5
mm, 21.2 mg; 4.3 mm, 36.4 mg; 4.1 mm, 30.0 mg. Therefore, the densities of the obtained particles are 0.945 and 0.945, respectively.
Calculated as 0.875, 0.832, true specific gravity of polystyrene
It can be seen that it is a highly densely packed body with a value close to 1.04.

Claims (1)

[Scope of Claims] 1 (A) A coagulant is added to an aqueous particle colloid that causes a coagulation reaction by adding a coagulant at a temperature lower than the temperature at which the colloid particles fuse together (softening temperature), and the coagulant is (B) The coagulant particles are coagulated on the outer surface of the coagulant particles, centering on the scattered coagulant units, and the coagulant particles are dispersed from the inside to the outside. (C) Separate the coagulated particles from the aqueous colloid to obtain coagulated particles; (D) From the softening temperature of the colloidal particles. By drying or heating in an aqueous phase while maintaining the temperature of the coagulated particles at a low temperature, coagulated particles tightly packed with colloidal particles constituting the coagulated particles are obtained, and (E) the coagulated particles are further softened. A method of obtaining a high-density spherical colloidal particle aggregate with an internal structure in which the colloidal particles are densely and homogeneously packed with no voids inside the particles by heating and melting the colloidal particles above the temperature. 2. The method according to claim 1, wherein the aqueous particle colloid is a polymer latex.