JP2021159788A - Method for producing granules and granules - Google Patents

Abstract

To provide a method for producing granules that can easily produce granules containing polymer fine particles without melting the polymer fine particles at high temperature.SOLUTION: A method for producing granules has a molding step for molding a granular material at 100°C or lower. The granular material contains polymer fine particles containing rubber-containing graft copolymers. The granular material contains powder with a particle size 50 μm or less, which constitutes at least 5 vol.% of the granular material 100 vol.%.SELECTED DRAWING: Figure 1

Description

The present invention relates to a method for producing granules and granules.

In order to improve the impact resistance of a thermoplastic resin or a thermosetting resin, a method of adding an elastomer, particularly polymer fine particles, to the resin is widely used.

Conventionally, as polymer fine particles to be added to a thermoplastic resin or a thermosetting resin, (a) a powder or granular material containing the polymer fine particles (Patent Document 1) or (b) a powder or granular material containing the polymer fine particles is used. A molten pellet containing polymer fine particles (Patent Document 2), which is formed while melting at a high temperature, is used.

Japanese Unexamined Patent Publication No. 2007-277368 Japanese Unexamined Patent Publication No. 11-080495

However, the above-mentioned prior art has room for further improvement from the viewpoints of handleability, complexity of the manufacturing process, and manufacturing cost.

One embodiment of the present invention has been made in view of the above problems, and an object of the present invention is to easily provide granules containing the polymer fine particles without melting the polymer fine particles at a high temperature.

As a result of diligent studies to solve the above problems, the present inventors have independently found the following points and have completed the present invention: a powder or granular material containing polymer fine particles and a particle diameter of 50 μm or less. In the case of a powder or granular material containing a specific amount of the powder of the above, the granules containing the polymer fine particles can be easily provided by molding the powder or granular material at a temperature of 100 ° C. or lower.

That is, one embodiment of the present invention includes the following configurations.
[1] The powder or granular material includes a molding step of molding the powder or granular material at a temperature of 100 ° C. or lower, the powder or granular material contains polymer fine particles containing a rubber-containing graft copolymer, and the powder or granular material is the powder or granular material. A method for producing granules, which comprises 5.0% by volume or more of powder having a particle size of 50 μm or less in 100% by volume of the body.
[2] The method for producing granules according to [1], wherein the powder or granular material has a D50 particle size of 400 μm or less.
[3] The method for producing a granule according to [1] or [2], wherein 10 or more voids having an area of 100 μm ^{2 or more are present in the fractured surface of the granule.}
[4] Prior to the molding step, a powder / granular material preparation step of obtaining a powder / granular material of the polymer fine particles from a latex containing the polymer fine particles is further included, and in the powder / granular material preparation step, the rubber-containing graft is used together. The method for producing granules according to any one of [1] to [3], wherein the polymer fine particles are handled at a temperature equal to or lower than the Vicat softening temperature of the polymer.
[5] Granules containing polymer fine particles containing a rubber-containing graft copolymer and having 10 or more voids having ^{an area of 100 μm 2 or more in a fractured surface.}

According to one embodiment of the present invention, granules containing the polymer fine particles can be easily provided without melting the polymer fine particles at a high temperature.

For Example 4, that is, the granules according to the embodiment of the present invention, the SEM image of the fractured surface obtained by imaging the fractured surface of the granule with a scanning electron microscope (SEM) and the SEM image are binarized. It is an image after processing. For the granules of Comparative Example 3, an SEM image of the fractured surface obtained by imaging the fractured surface of the granule with a scanning electron microscope (SEM) and an image obtained by binarizing the SEM image.

An embodiment of the present invention will be described below, but the present invention is not limited thereto. The present invention is not limited to the configurations described below, and various modifications can be made within the scope of the claims. The technical scope of the present invention also includes embodiments or examples obtained by appropriately combining the technical means disclosed in the different embodiments or examples. Furthermore, new technical features can be formed by combining the technical means disclosed in each embodiment. In addition, all the academic documents and patent documents described in the present specification are incorporated as references in the present specification. Further, unless otherwise specified in the present specification, "A to B" representing a numerical range is intended to be "A or more (including A and larger than A) and B or less (including B and smaller than B)".

[1. Technical Thought of One Embodiment of the Present Invention]
As a result of examination by the present inventors, it was found that the prior arts such as Patent Documents 1 and 2 have the following room for improvement.

That is, the powder or granular material containing the polymer fine particles as in Patent Document 1 is inferior in handleability as compared with a substance having a larger volume per particle than the powder or granular material such as granules. As a technique in which the handling of the polymer fine particles is better than that of the technique of Patent Document 1, a melt containing the polymer fine particles is formed by molding the powder or granular material containing the polymer fine particles at a high temperature as in Patent Document 2. Pellets are known. However, the present inventors need to melt the polymer fine particles (powder and granular material) at a high temperature in a technique such as Patent Document 2, and therefore require complicated equipment represented by a twin-screw extruder. Since it is a technology, we have independently found that there are the following problems: (a) the manufacturing process is complicated, and (b) the introduction cost, operation cost, maintenance cost, etc. of complicated equipment, etc. Therefore, the manufacturing cost becomes high.

Therefore, the present inventors aim to provide granules containing the polymer fine particles easily, for example, by using a small molding machine used for a general resin, without melting the polymer fine particles at a high temperature. As a result, we conducted a diligent study. As a result, the present inventors have independently found the following points and have completed the present invention: a powder or granular material containing polymer fine particles and containing a specific amount of powder having a particle diameter of 50 μm or less. In the case of granules, granules containing polymer fine particles can be easily provided by molding the powder or granular material at a temperature of 100 ° C. or lower without melting the powder or granular material at a high temperature.

Here, if it is a powder or granular material containing a specific amount of powder having a particle diameter of 50 μm or less, the reason why the granules can be easily obtained from the powder or granular material is not clear, but it can be inferred as follows, for example. That is, a powder containing a powder having a particle size of 50 μm or less (hereinafter, also referred to as powder A) and a powder and / or a particle having a particle size larger than 50 μm (hereinafter, also referred to as powder / particle B). When the granules are formed into granules, the powder A can enter between the powder / the granules B. As a result, it is presumed that (a) a close-packed structure is formed and (b) the shape of the granules is maintained. It should be noted that one embodiment of the present invention is not limited to such speculation.

[2. Granule manufacturing method]
The method for producing granules according to an embodiment of the present invention includes a molding step of molding a powder or granular material at a temperature of 100 ° C. or lower, and the powder or granular material contains polymer fine particles containing a rubber-containing graft copolymer. The powder or granular material contains 5.0% by volume or more of powder having a particle diameter of 50 μm or less in 100% by volume of the powder or granular material. The granules obtained by the method for producing granules according to the embodiment of the present invention become a resin composition by being dispersed in a matrix resin described later.

In the present specification, "a method for producing granules according to an embodiment of the present invention" may be referred to as "the present production method". In the present specification, the "polymer fine particles" may be referred to as "polymer fine particles (A)", and the "matrix resin" may be referred to as "matrix resin (C)".

By having the above-mentioned structure, the present production method has an advantage that granules containing the polymer fine particles (A) can be easily provided without melting the polymer fine particles (A) at a high temperature. .. Granules have the advantages of (a) being less likely to scatter and being less likely to adhere to the body and devices, and are easier to handle than powder granules, and (b) being mixed with the granular matrix resin (C). It has the advantage of being easy to classify (difficult to classify). Further, in this production method, since the polymer fine particles (A) are not melted at a high temperature, the heat load on the polymer fine particles (A) is small. Therefore, according to this production method, granules with less coloring can be obtained without using a heat stabilizer. The "heat load on the polymer fine particles (A)" can also be said to be "giving a thermal history to the polymer fine particles (A)" or "thermal deterioration of the polymer fine particles (A)".

(2-1. Molding process)
The molding step is a step of molding the powder or granular material into granules at a temperature of 100 ° C. or lower by using, for example, a molding apparatus.

The prior art requires the polymer fine particles (granular materials) to be melted at a high temperature, and therefore requires a complex device as a molding device having a plurality of facilities as listed below: ( (a) Large motor power capable of providing shear rate and torque to melt polymer fine particles (granular material), (b) Long screw allowing large amount of polymer fine particles (granular material) to be melted, ( c) Equipment for handling the melt of polymer fine particles (powder and granular material) (for example, heat-resistant equipment), and (d) Equipment for cooling the melt (for example, a cooling tank). Such complex devices include twin-screw extruders and squeezing dehydrators. In the prior art, in addition to the complicated process of melting the polymer fine particles (powder and granular material), (a) the introduction cost of the complicated equipment described above, and (b) the operation and maintenance (for example, disassembly and cleaning and repair). The load of time and cost for this is high.

On the other hand, in this production method, it is not necessary to melt the polymer fine particles (A) (powder / granules) at a high temperature, and therefore the polymer fine particles (A) can be obtained by using a simple molding apparatus as compared with the conventional technique. ) Can be obtained. Equipment that can be used in this manufacturing method includes, for example, a wet extrusion granulator (for example, (a) a pelleter double manufactured by Dalton Corporation and (b) a gear pelletizer manufactured by Hosokawa Micron Corporation / Bepex Co., Ltd.) and a small molding machine. (For example, an HG type cylindrical granulator manufactured by Hata Iron Works Co., Ltd.) and the like are preferably mentioned.

The configuration "at a temperature of 100 ° C. or lower" is intended to handle the powder or granular material at a temperature of 100 ° C. or lower throughout the molding process, in other words, the powder or granular material is exposed to a temperature environment of more than 100 ° C. Intended to never happen. Therefore, the rubber-containing graft copolymer and the polymer fine particles (A) are also handled at a temperature of 100 ° C. or lower and are not exposed to a temperature environment of more than 100 ° C. throughout the molding process. In the present specification, the temperature at which the powder or granular material is handled throughout the molding process may be referred to as "molding temperature".

The molding temperature is preferably less than 100 ° C., more preferably 80 ° C. or lower, further preferably 60 ° C. or lower, and particularly preferably 40 ° C. or lower. According to this configuration, the cost for heating can be reduced, so that the granules can be obtained at low cost. Further, according to this configuration, since the heat load on the polymer fine particles (A) is smaller, granules with less coloring can be obtained without using a heat stabilizer. The lower limit of the molding temperature is not particularly limited, but it is preferable to mold the powder or granular material at a temperature at which the powder or granular material does not freeze. In order to keep the temperature at which the powder or granular material is handled within the above range, for example, a method of setting the temperature inside the molding apparatus used in the molding step within the above range can be mentioned.

In the molding step, the molding time is not particularly limited, but a shorter molding time is preferable in order to obtain granules at a lower cost. Examples of the molding time include the time for the powder or granular material to stay in the molding apparatus. The molding time is preferably 5 minutes or less, more preferably 4 minutes or less, and particularly preferably 3 minutes or less. According to this structure, granules can be obtained at low cost. Further, according to this configuration, since the heat load on the polymer fine particles (A) is smaller, granules with less coloring can be obtained without using a heat stabilizer.

In the molding step, pressure may be applied to the powder or granular material, in other words, the powder or granular material may be compressed. Examples of the method of applying pressure to the powder or granular material include a method of adjusting the amount of the powder or granular material supplied to the molding apparatus per unit time and the amount of the granules discharged from the molding apparatus per unit time. The higher the amount of powder or granular material supplied to the molding apparatus per unit time and / or the smaller the amount of granules discharged from the molding apparatus per unit time, the higher the pressure applied to the powder or granular material. can.

In the molding step, the pressure applied to the powder or granular material is not particularly limited and may be appropriately set. (A) Amount of powder or granular material supplied to the molding apparatus, (b) Volume inside the molding apparatus (amount of powder or granular material processed), (c) Length of the die provided in the molding apparatus in the extrusion direction ("Die" (Sometimes referred to as "plate thickness" or "plate thickness"), (d) the hole diameter of the discharge hole provided in the die, (e) the area (opening ratio) of the discharge hole, (f). ) The pressure applied to the powder or granular material can be adjusted by the distance between the centers of the discharge holes (sometimes referred to as "hole pitch") and (g) the discharge amount of the molded powder or granular material.

(2-2. Powder and granule preparation process)
The present production method preferably further includes a powder or granular material preparation step of obtaining powder or granular material of the polymer fine particles (A) from the latex containing the polymer fine particles (A) before the molding step. The "latex containing the polymer fine particles (A)" may be simply referred to as "latex" below. It can be said that the powder / granular material preparation step is a step of obtaining a powder / granular material obtained by agglutinating the polymer fine particles (A) using latex. That is, the powder or granular material in one embodiment of the present invention is (a) a powder or granular material formed by aggregating polymer fine particles, and (b) a powder or granular material containing an aggregate containing the polymer fine particles (A). It can be said that.

The solvent in the latex is not particularly limited, but it is preferably an aqueous solvent containing water, and particularly preferably water. That is, the latex containing the polymer fine particles (A) is particularly preferably an aqueous latex containing the polymer fine particles (A).

In the powder / granule preparation step, it is preferable to handle the polymer fine particles (A) at a temperature equal to or lower than the Vicat softening temperature of the rubber-containing graft copolymer contained in the polymer fine particles (A). According to this configuration, it is possible to obtain a powder or granular material having a wide particle size distribution of the volume average particle size, in other words, it is possible to obtain a powder or granular material containing a large amount of powder having a particle size of 50 μm or less. As a result, granules can be more easily obtained from the obtained powder or granular material, for example, the obtained powder or granular material can be molded into granules at a lower molding temperature and a lower molding pressure. Further, in the powder / granular body preparation step, when the polymer fine particles (A) are handled at a temperature equal to or lower than the Vicat softening temperature of the rubber-containing graft copolymer contained in the polymer fine particles (A), the polymer fine particles (A) are subjected to. The heat load is reduced, and the fusion of the polymer fine particles (A) to each other can be eliminated. As a result, (a) granules with less coloring can be obtained without using a heat stabilizer, and (b) the resin composition containing the obtained granules is a polymer fine particle in the matrix resin (C). It has the advantage that the dispersibility of (A) becomes more excellent. When the polymer fine particles (A) contain a plurality of types of rubber-containing graft copolymers, in the powder / granule preparation step, each of the plurality of types of rubber-containing graft copolymers contained in the polymer fine particles (A) is bicut. It is preferable to handle the polymer fine particles (A) at a temperature equal to or lower than the lowest Vicat softening temperature among the softening temperatures.

In the powder / granule preparation step, it is more preferable to handle the polymer fine particles (A) at a Vicat softening temperature of -4 ° C. or lower, which is a Vicat softening temperature of −8, of the rubber-containing graft copolymer contained in the polymer fine particles (A). It is more preferable to handle it at ° C. or lower, and it is particularly preferable to handle it at a Vicat softening temperature of −12 ° C. or lower. According to this configuration, (a) granules with less coloring can be obtained more easily without using a heat stabilizer, and (b) the resin composition containing the obtained granules is a matrix resin (C). ) Has the advantage that the dispersibility of the polymer fine particles (A) is further improved.

In the powder or granular material preparation step, the specific method for preparing the powder or granular material is not particularly limited. Examples of the method for preparing the powder or granular material include a slurry preparation step of preparing a slurry containing an aggregate of the polymer fine particles (A) from a latex containing the polymer fine particles (A), and a slurry preparation step of preparing water from the slurry. Examples thereof include a dehydration step of removing components and recovering the agglomerates.

(2-2-1. Slurry preparation process)
The slurry preparation step is a step of preparing a mixture containing an aggregate containing the polymer fine particles (A) and an aqueous solvent from latex, that is, a slurry. The slurry preparation step can be said to be (a) a step of preparing agglomerates of polymer fine particles (A) using latex, and (b) a step of aggregating polymer fine particles (A) in latex.

The method for agglutinating the polymer fine particles (A) is not particularly limited. Examples of the method include (a) a method of bringing the latex into contact (for example, mixing) with an aqueous solution containing an agglutinant and / or an agglutinant, and (b) a method of bringing the latex into a highly hydrophobic organic solvent (for example, methyl ethyl ketone). Known methods such as (c) a method of freezing the latex and then thawing, (d) a method of applying shear stress to the latex, and (e) a method of spraying the latex.

The slurry preparation step, specifically, the aggregation of the polymer fine particles (A) is preferably carried out in the presence of an antiblocking agent. According to this structure, the blocking resistance is improved, and the dispersibility of the polymer fine particles (A) in the matrix resin (C) is further improved in the obtained resin composition containing the granules. Has advantages.

In the slurry preparation step, by appropriately setting the temperature, time, stirring number, etc. at the time of slurry preparation, (a) the amount of powder having a particle size of 50 μm or less contained in the powder or granular material, and (b) the powder or granular material The water content can be adjusted.

The temperature at the time of preparing the slurry is (a1) the ambient temperature when the slurry preparation step is carried out (for example, the room temperature of the work space), (b1) the temperature of the latex, and (c1) the flocculant when a flocculant is used. And / or the temperature of the aqueous solution containing the flocculant, or the temperature of the mixture of the latex and the coagulant and / or the aqueous solution containing the flocculant, (d1) When the latex is frozen, when the frozen latex is thawed. Temperature (thawing temperature), (e1) the temperature of the latex when the shear stress is applied, and (f1) when the latex is sprayed, when the latex is sprayed. The temperature of the latex, the temperature of the latex after being sprayed, and the like. As the time for preparing the slurry, (a) the time for the slurry preparation step, (b) the time for holding the latex at a predetermined temperature, and (c) a mixture of the latex and an aqueous solution containing a coagulant and / or a coagulant are predetermined. Time to keep at the temperature of, (d) stirring time of the mixture when stirring the mixture, (e) freezing time of latex when freezing latex, and thawing time of frozen latex (freezing). Examples include (f) time for exposing the latex to the thawing temperature), (f) time for applying shear stress to the latex (time for shearing (stirring) the latex), and the like. The number of stirrings at the time of preparing the slurry is (a) the number of stirrings of latex, (b) the number of stirrings of a mixture of latex and an aqueous solution containing a flocculant and / or coagulant when a flocculant is used, and (c). ) When a shear stress is applied to the latex, the number of times the latex is agitated when the shear stress is applied, and the like can be mentioned. The temperature, time, and the number of stirrings at the time of preparing the slurry in the slurry preparation step depend on (a) the amount of powder having a particle size of 50 μm or less contained in the powder or granular material and (b) the water content of the powder or granular material. It can be set as appropriate.

When the polymer fine particles (A) are handled at a temperature equal to or lower than the Vicat softening temperature of the rubber-containing graft copolymer in the powder / granule preparation step, the rubber-containing temperatures (a1) to (f1) are set in the slurry preparation step. The temperature may be set to a temperature equal to or lower than the Vicat softening temperature of the graft copolymer. The temperatures of these (a1) to (f1) in the slurry preparation step are preferably temperatures equal to or lower than the Vicat softening temperature of the rubber-containing graft copolymer. According to this configuration, (a) granules with less coloring can be obtained more easily without using a heat stabilizer, and (b) the resin composition containing the obtained granules is a matrix resin (C). ) Has the advantage that the dispersibility of the polymer fine particles (A) is further improved.

The temperature of the aqueous solution containing the agglutinant and / or the agglutinant or the temperature of the mixture of the latex and the aqueous solution containing the agglutinant and / or the agglutinant will be described in (c1) above. These temperatures are not particularly limited, but are preferably 25 ° C to 85 ° C, more preferably 30 ° C to 80 ° C, more preferably 35 ° C to 70 ° C, more preferably 40 ° C to 70 ° C, and more preferably 45 ° C to 70 ° C. Is more preferable, and 50 ° C. to 65 ° C. is particularly preferable.

(2-2-2. Dehydration process)
The dehydration step is a step of removing the water component from the slurry by separating the aqueous solvent of the slurry and the agglomerates, and recovering the agglomerates. The slurry in the dehydration step may be (a) a slurry obtained in the slurry preparation step, or (b) a slurry containing washed aggregates obtained in the washing step described later. ..

The method for separating the aqueous solvent of the slurry and the aggregate is not particularly limited, and a known method can be used. Examples of the method for separating the aqueous solvent of the slurry and the aggregate include a method of filtering the slurry (for example, suction filtration), a method of centrifuging the slurry, and the like.

In the dehydration step, by appropriately setting the conditions for filtering the slurry and the conditions for centrifuging the slurry, (a) the amount of powder having a particle size of 50 μm or less contained in the powder or granular material, and (b) The water content of the powder or granular material can be adjusted.

Conditions for filtering the slurry include the roughness of the filter used. Further, when the slurry is suction-filtered, the degree of vacuum and the suction time at the time of sucking the slurry can be mentioned. Conditions for centrifuging the slurry include the rotational speed of the centrifuge, the centrifugal force (g), and the centrifugal (rotation) time. The conditions for filtering the slurry and for centrifuging the slurry depend on (a) the amount of powder having a particle size of 50 μm or less contained in the powder or granular material and (b) the water content of the powder or granular material. Can be set as appropriate.

When the polymer fine particles (A) are handled at a temperature equal to or lower than the Vicat softening temperature of the rubber-containing graft copolymer in the powder / granule preparation step, the temperature of the slurry and the water component (for example, the water component after centrifugation) are used in the dehydration step. The temperature of the agglomerates, the temperature of the agglomerates (for example, the agglomerates after centrifugation), and the like may be set to a temperature equal to or lower than the Vicat softening temperature of the rubber-containing graft copolymer. The temperature of the slurry, the temperature of the water component, and the temperature of the aggregate in the dehydration step are preferably temperatures equal to or lower than the Vicat softening temperature of the rubber-containing graft copolymer. According to this configuration, (a) granules with less coloring can be obtained more easily without using a heat stabilizer, and (b) the resin composition containing the obtained granules is a matrix resin (C). ) Has the advantage that the dispersibility of the polymer fine particles (A) is further improved.

The agglomerates recovered in the dehydration step can be used as powder or granular materials, and the agglomerates recovered in the dehydration step can be further subjected to a washing step and / or a drying step described later, and the agglomerates obtained can be obtained as powder or granular materials. It can also be a body.

(2-2-3. Resin mixing process)
The powder / granule preparation step may include a resin mixing step of mixing the resin with the latex containing the polymer fine particles (A) before or during the slurry preparation step. The resin mixed with latex in the resin mixing step may be hereinafter referred to as "resin (B)". The resin mixing step can also be said to be a step of adding the resin (B) to the latex containing the polymer fine particles (A) and mixing them to obtain the latex containing the polymer fine particles (A) and the resin (B).

When the powder or granular material preparation step includes a resin mixing step, the obtained powder or granular material may contain polymer fine particles (A) and resin (B). When the obtained powder or granular material contains the polymer fine particles (A) and the resin (B), the powder or granular material can be said to be an agglomerate containing the polymer fine particles (A) and the resin (B), and the polymer fine particles (A). ) And the aggregated particles of the resin (B). When the powder or granular material preparation step includes a resin mixing step, the obtained granules may contain polymer fine particles (A) and resin (B).

In the resin mixing step, various methods can be used for adding the resin (B) to the latex containing the polymer fine particles (A), and the method is not particularly limited. For example, (a) a method of directly adding the resin (B) to the latex containing the polymer fine particles (A), and (b) the resin (B) being heavily emulsified with water (aqueous emulsion state). Examples thereof include a method of adding to the latex containing the coalesced fine particles (A), and a method of adding (c) to the latex containing the polymer fine particles (A) in a solution state in which the resin (B) is dissolved. Among them, a method of adding the resin (B) to the latex containing the polymer fine particles (A) in a state of being emulsified with water in advance (aqueous emulsion state) is preferable.

Further, the method of mixing the latex containing the polymer fine particles (A) and the resin (B) is not particularly limited. For example, a method of (a) stirring the mixture obtained by adding the resin (B) to the latex containing the polymer fine particles (A), and (b) a method of kneading with a continuous kneader can be mentioned. ..

When the polymer fine particles (A) are handled at a temperature equal to or lower than the vicut softening temperature of the rubber-containing graft copolymer in the powder / granule preparation step, the following temperature is set to the vicut softening temperature of the rubber-containing graft copolymer in the resin mixing step. The temperature may be equal to or lower than the temperature: (a) the temperature of the latex containing the polymer fine particles (A), (b) the temperature of the resin (B) (the emulsified state (aqueous emulsion state) of the resin (B) (resin). (Including the temperature of the aqueous emulsion of (B)) and the temperature of the solution of the resin (B) in which the resin (B) is dissolved), (c) The latex containing the polymer fine particles (A) and the resin (B) Atmospheric temperature when mixing (temperature under working environment and temperature inside the mixing device, etc.), etc. The temperatures of these (a) to (c) in the resin mixing step are preferably temperatures equal to or lower than the Vicat softening temperature of the rubber-containing graft copolymer. According to this configuration, (a) granules with less coloring can be obtained more easily without using a heat stabilizer, and (b) the resin composition containing the obtained granules is a matrix resin (C). ) Has the advantage that the dispersibility of the polymer fine particles (A) is further improved.

(2-2-4. Cleaning process)
The powder / granule preparation step may include (a) a washing step of washing the aggregates in the slurry obtained in the slurry preparation step before the dehydration step, and / or (b) the dehydration step. After, a washing step of washing the agglomerates recovered in the dehydration step may be included. By washing the agglomerates, powders and granules having a lower content of impurities and the like can be obtained. In the washing step, it is more preferable to wash the agglomerates with water, and it is further preferable to wash the agglomerates with ion-exchanged water or pure water.

The washing step may be a step of washing the agglomerates, and the specific method is not particularly limited. For example, a method of mixing agglomerates and water and stirring them with a stirrer, a method of kneading agglomerates and water using a kneader, a method of mixing agglomerates and water with a rotation / revolution mixer, and a method of mixing water into agglomerates. Examples thereof include a method of spraying, a method of washing the agglomerates with a pressure filter, and the like. As the kneader, various types such as a batch type kneader, a continuous type kneader, and an extrusion type kneader can be used.

By appropriately setting the cleaning temperature (also referred to as "cleaning water temperature"), cleaning time, number of cleanings, etc. in the cleaning step, (a) the amount of powder having a particle size of 50 μm or less contained in the obtained powder or granular material. , And (b) the water content of the obtained powder or granular material can be adjusted.

The cleaning temperature is not particularly limited. As the washing water, for example, normal temperature water or heated hot water can be appropriately used. Since the cleaning effect is higher in warm water, it is preferable to use heated cleaning water from the viewpoint of cleaning effect. When the polymer fine particles (A) are handled at a temperature equal to or lower than the Vicat softening temperature of the rubber-containing graft copolymer in the powder / granule preparation step, the washing temperature is set to be equal to or lower than the Vikat softening temperature of the rubber-containing graft copolymer in the washing step. The temperature should be set to. The cleaning temperature is appropriately set according to desired values such as (a) the amount of powder having a particle diameter of 50 μm or less contained in the powder or granular material and (b) the water content of the obtained powder or granular material. May be good.

The washing temperature is preferably a temperature equal to or lower than the Vicat softening temperature of the rubber-containing graft copolymer. According to this configuration, (a) granules with less coloring can be obtained more easily without using a heat stabilizer, and (b) the resin composition containing the obtained granules is a matrix resin (C). ) Has the advantage that the dispersibility of the polymer fine particles (A) is further improved.

The cleaning temperature can be, for example, 10 ° C. to 100 ° C., preferably 15 ° C. to 100 ° C., more preferably 20 ° C. to 100 ° C., and preferably 40 ° C. to 100 ° C. It is even more preferably 40 ° C to 80 ° C, even more preferably 40 ° C to 70 ° C. The cleaning temperature may be 15 ° C. to 90 ° C. or 20 ° C. to 85 ° C. The cleaning temperature is preferably less than 90 ° C, more preferably less than 80 ° C, and even more preferably less than 70 ° C. According to this structure, the resin composition containing the obtained granules has further excellent dispersibility of the polymer fine particles (A) in the matrix resin (C).

The washing time of the agglomerates is not particularly limited, and depends on desired values such as (a) the amount of powder having a particle size of 50 μm or less contained in the powder or granular material, and (b) the water content of the obtained powder or granular material. , Can be set as appropriate. The washing time can be, for example, 1 second to 60 minutes, preferably 1 second to 45 minutes, more preferably 1 minute to 30 minutes, and 3 minutes to 30 minutes. More preferably, it is particularly preferably 5 minutes to 30 minutes. The washing time may be 10 to 30 minutes or 5 to 10 minutes.

The number of times the agglomerates are washed is not particularly limited, and depends on desired values such as (a) the amount of powder having a particle size of 50 μm or less contained in the powder or granular material, and (b) the water content of the obtained powder or granular material. , Can be set as appropriate. The number of washings can be, for example, 1 to 10 times (cycles), but is preferably 1 to 6 times (cycles), more preferably 1 to 5 times (cycles), and 1 It is more preferably 1 to 4 times (cycle), and particularly preferably 1 to 3 times (cycle).

The amount of wash water is not particularly limited, and for example, it may be 0.1 parts by weight to 1000 parts by weight with respect to 1 part by weight of the aggregate, but it may be 1 part by weight to 500 parts by weight. It is more preferably 1 part by weight to 200 parts by weight, further preferably 1 part by weight to 10 parts by weight, and particularly preferably 2 parts by weight to 10 parts by weight. The amount of wash water may be 15 parts by weight to 500 parts by weight or 2 to 5 parts by weight with respect to 1 part by weight of the aggregate. Further, when washing by kneading with a kneader, the amount of washing water can be reduced, which is more preferable.

Further, the method of removing the washed water is not limited, and the same method as the dehydration method in the dehydration step can be mentioned. Specific examples of the method for removing the washed water include methods such as discharge of washed water, vacuum filtration, oil-water separation, filter press, belt press, screw press, membrane separation, centrifugal dehydration and squeeze dehydration. When the dehydration step is performed after the washing step, it is not necessary to remove the washed water after the final washing in the washing step, and the slurry containing the washed aggregates can be subjected to the dehydration step.

The object to be washed is intended to be all impurities contained in the agglomerate, and is not particularly limited. Examples of the object to be washed include impurities derived from emulsifiers (for example, phosphorus-based emulsifiers and sulfonic acid-based emulsifiers), and when a coagulant described later is used, impurities derived from the coagulant and the like can be mentioned. can.

The agglomerates washed in the washing step can be used as powder or granular materials, and the agglomerates washed in the washing step can be further subjected to a drying step described later to be used as powder or granular materials. can.

(2-2-5. Drying process)
The powder / granule preparation step may include a drying step of drying the agglomerates recovered in the dehydration step or the agglomerates obtained through the dehydration step and the washing step. The aggregates dried in the drying step can also be made into powder or granular materials.

The drying step is not particularly limited as long as the agglomerates can be dried. The method for drying the agglomerates is not particularly limited, and the method for drying the agglomerates using a dryer, the method for charging the agglomerates in the container and heating and depressurizing the inside of the container, and the method for charging the agglomerates in the container and the container concerned. Examples thereof include a method in which the dry gas and the agglomerate are brought into countercurrent contact with each other.

By appropriately setting the drying temperature, drying time, etc. in the drying step, (a) the amount of powder having a particle size of 50 μm or less contained in the obtained powder or granular material, and (b) the water content of the obtained powder or granular material. Etc. can be adjusted.

The drying temperature in the drying step, for example, the temperature inside the dryer or the temperature of the drying gas is not particularly limited, and (a) (a-1) a desired amount of powder having a particle size of 50 μm or less contained in the powder or granular material. And (a-2) a desired amount such as a desired water content of the powder or granular material, and (b) a production cost and the like, it can be appropriately set according to the drying time.

The drying temperature in the drying step is, for example, preferably less than 90 ° C, more preferably less than 80 ° C, more preferably less than 70 ° C, more preferably less than 60 ° C, more preferably less than 50 ° C, still more preferably less than 40 ° C.

When the polymer fine particles (A) are handled at a temperature equal to or lower than the Vicat softening temperature of the rubber-containing graft copolymer in the powder / granule preparation step, the drying temperature is set to be equal to or lower than the Vikat softening temperature of the rubber-containing graft copolymer in the drying step. The temperature should be set to. The drying temperature is preferably a temperature equal to or lower than the Vicat softening temperature of the rubber-containing graft copolymer. According to this configuration, (a) granules with less coloring can be obtained more easily without using a heat stabilizer, and (b) the resin composition containing the obtained granules is a matrix resin (C). ) Has the advantage that the dispersibility of the polymer fine particles (A) is further improved.

The drying time in the drying step is not particularly limited, and (a) (a-1) a desired amount of powder having a particle size of 50 μm or less contained in the powder or granular material, and (a-2) desired water content of the powder or granular material. It can be appropriately set according to the drying temperature from the viewpoint of a desired amount such as rate and (b) production cost.

(2-3. Polymer fine particles (A))
The polymer fine particles (A) may be fine particles obtained by polymerization and may contain a rubber-containing graft copolymer, and other configurations are not particularly limited. The rubber-containing graft copolymer has an elastic body and a graft portion graft-bonded to the elastic body.

(2-3-1. Elastic body)
The elastic body preferably contains at least one selected from the group consisting of a diene-based rubber, a (meth) acrylate-based rubber, and a polysiloxane rubber-based elastic body. The elastic body can also be rephrased as rubber particles.

A case where the elastic body contains a diene rubber (case A) will be described. In Case A, the obtained resin composition containing granules can provide a cured product or a molded product having excellent toughness and impact resistance.

The diene-based rubber is an elastic body containing a structural unit derived from a diene-based monomer as a structural unit. The diene-based monomer can also be rephrased as a conjugated diene-based monomer. In Case A, the diene-based rubber contains 50 to 100% by weight of the constituent unit derived from the diene-based monomer in 100% by weight of the constituent unit, and other than the diene-based monomer copolymerizable with the diene-based monomer. It may contain 0 to 50% by weight of a structural unit derived from the vinyl-based monomer of. In Case A, the diene-based rubber may contain a structural unit derived from the (meth) acrylate-based monomer as a structural unit in a smaller amount than the structural unit derived from the diene-based monomer.

Examples of the diene-based monomer include 1,3-butadiene, isoprene, 2-chloro-1,3-butadiene, 2-methyl-1,3-butadiene and the like. Only one kind of these diene-based monomers may be used, or two or more kinds thereof may be used in combination.

Examples of the vinyl-based monomer (hereinafter, also referred to as vinyl-based monomer A) other than the diene-based monomer copolymerizable with the diene-based monomer include styrene, α-methylstyrene, and monochlorostyrene. , Vinyl allenes such as dichlorostyrene; Vinyl carboxylic acids such as acrylic acid and methacrylic acid; Vinyl cyanides such as acrylonitrile and methacrylate; Vinyl halides such as vinyl chloride, vinyl bromide and chloroprene; Vinyl acetate; Ethylene , Alkens such as propylene, butylene, isobutylene; polyfunctional monomers such as diallylphthalate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, and the like. As the vinyl-based monomer other than the diene-based monomer described above, only one type may be used, or two or more types may be used in combination. Among the vinyl-based monomers other than the diene-based monomer described above, styrene is particularly preferable. In the diene-based rubber in Case A, the structural unit derived from the vinyl-based monomer other than the diene-based monomer is an optional component. In Case A, the diene-based rubber may be composed of only the structural units derived from the diene-based monomer.

In Case A, as the diene rubber, butadiene rubber (also referred to as polybutadiene rubber) composed of a structural unit derived from 1,3-butadiene, or butadiene-, which is a copolymer of 1,3-butadiene and styrene. Styrene rubber (also referred to as polystyrene-butadiene) is preferable, and butadiene rubber is more preferable. According to the above configuration, the desired effect due to the polymer fine particles (A) containing the diene rubber can be more exhibited. Further, butadiene-styrene rubber is more preferable in that the transparency of the obtained cured product or molded product can be enhanced by adjusting the refractive index.

The case where the elastic body contains (meth) acrylate-based rubber (case B) will be described. In case B, a wide range of polymer designs of elastic bodies is possible by combining various monomers.

The (meth) acrylate-based rubber is an elastic body containing a structural unit derived from the (meth) acrylate-based monomer as a structural unit. In Case B, the (meth) acrylate-based rubber contains 50 to 100% by weight of the constituent unit derived from the (meth) acrylate-based monomer in 100% by weight of the constituent unit, and is copolymerized with the (meth) acrylate-based monomer. It may contain 0 to 50% by weight of a structural unit derived from a vinyl-based monomer other than the polymerizable (meth) acrylate-based monomer. In Case B, the (meth) acrylate-based rubber may contain, as the structural unit, a structural unit derived from the diene-based monomer in a smaller amount than the structural unit derived from the (meth) acrylate-based monomer. good.

Examples of the (meth) acrylate-based monomer include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, and dodecyl (meth) acrylate. Alkyl (meth) acrylates such as stearyl (meth) acrylate and behenyl (meth) acrylate; aromatic ring-containing (meth) acrylates such as phenoxyethyl (meth) acrylate and benzyl (meth) acrylate; 2-hydroxyethyl (meth) ethyl. ) Hydroxyalkyl (meth) acrylates such as acrylates and 4-hydroxybutyl (meth) acrylates; glycidyl (meth) acrylates such as glycidyl (meth) acrylates and glycidylalkyl (meth) acrylates; alkoxyalkyl (meth) acrylates; Allylalkyl (meth) acrylates such as allyl (meth) acrylate and allylalkyl (meth) acrylate; monoethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate and the like. Examples thereof include polyfunctional (meth) acrylates. Only one kind of these (meth) acrylate-based monomers may be used, or two or more kinds thereof may be used in combination. Among these (meth) acrylate-based monomers, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate are particularly preferable.

A vinyl monomer other than the (meth) acrylate-based monomer copolymerizable with the (meth) acrylate-based monomer (hereinafter, also referred to as a vinyl-based monomer other than the (meth) acrylate-based monomer). ) Examples include the monomers listed in the vinyl-based monomer A. As the vinyl-based monomer other than the (meth) acrylate-based monomer, only one kind may be used, or two or more kinds may be used in combination. Among vinyl-based monomers other than the (meth) acrylate-based monomer, styrene is particularly preferable. In the (meth) acrylate-based rubber in Case B, the structural unit derived from the vinyl-based monomer other than the (meth) acrylate-based monomer is an optional component. In Case B, the (meth) acrylate-based rubber may be composed of only the structural units derived from the (meth) acrylate-based monomer.

A case where the elastic body includes a polysiloxane rubber-based elastic body (case C) will be described. In Case C, the obtained resin composition containing granules can provide a cured product or a molded product having sufficient heat resistance and excellent impact resistance at a low temperature.

The polysiloxane rubber-based elastic body is composed of alkyl or aryl disubstituted silyloxy units such as (a) dimethylsilyloxy, diethylsilyloxy, methylphenylsilyloxy, diphenylsilyloxy, and dimethylsilyloxy-diphenylsilyloxy. Polysiloxane-based polymer to be produced, (b) Polysiloxane-based polymer composed of alkyl or aryl1-substituted silyloxy units, such as (b) organohydrogensilyloxy in which a part of alkyl in the side chain is substituted with a hydrogen atom. Can be mentioned. Only one kind of these polysiloxane-based polymers may be used, or two or more kinds thereof may be used in combination. Among these polysiloxane-based polymers, (a) the resin composition containing the obtained granules can provide a cured product or a molded product having excellent heat resistance. And / or a polymer composed of dimethylsilyloxy-diphenylsilyloxy units is preferred, and (b) a polymer composed of dimethylsilyloxy units is most preferred because it is readily available and economical.

In Case C, the polymer fine particles (A) preferably contain 80% by weight or more of the polysiloxane rubber-based elastic body in 100% by weight of the elastic body contained in the polymer fine particles (A), preferably 90% by weight. It is more preferable that the above content is contained. According to the above structure, the resin composition containing the obtained granules can provide a cured product or a molded product having excellent heat resistance.

The elastic body may further include an elastic body other than the diene-based rubber, the (meth) acrylate-based rubber, and the polysiloxane rubber-based elastic body. Examples of the elastic body other than the diene-based rubber, the (meth) acrylate-based rubber, and the polysiloxane rubber-based elastic body include natural rubber.

(Cross-linked structure of elastic body)
From the viewpoint of maintaining the dispersion stability of the polymer fine particles (A) in the thermosetting resin or the thermoplastic resin, it is preferable that the elastic body has a crosslinked structure. As a method for introducing the crosslinked structure into the elastic body, a generally used method can be adopted, and examples thereof include the following methods. That is, in the production of an elastic body, there is a method in which a cross-functional monomer such as a polyfunctional monomer and / or a mercapto group-containing compound is mixed with a monomer that can form an elastic body, and then polymerized. .. In the present specification, producing a polymer such as an elastic body is also referred to as polymerizing a polymer.

In addition, as a method for introducing a crosslinked structure into a polysiloxane rubber-based elastic body, the following methods can also be mentioned: (a) When polymerizing a polysiloxane rubber-based elastic body, a polyfunctional alkoxysilane compound is used. A method of partially using it together with other materials, (b) introducing a reactive group such as a vinyl-reactive group or a mercapto group into a polysiloxane rubber-based elastic body, and then introducing a vinyl-polymerizable monomer or an organic peroxide, etc. Or when polymerizing a polysiloxane rubber-based elastic body, a crosslinkable monomer such as a polyfunctional monomer and / or a mercapto group-containing compound is used as another material. A method of mixing with and then polymerizing, etc.

A polyfunctional monomer can be said to be a monomer having two or more radically polymerizable reactive groups in the same molecule. The radically polymerizable reactive group is preferably a carbon-carbon double bond. Examples of the polyfunctional monomer include (meth) acrylates that do not contain butadiene and have an ethylenically unsaturated double bond, such as allylalkyl (meth) acrylates and allyloxyalkyl (meth) acrylates. Will be done. Examples of the monomer having two (meth) acrylic groups include ethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, and cyclohexanedimethanol. Di (meth) acrylates and polyethylene glycol di (meth) acrylates can be mentioned. Examples of the polyethylene glycol di (meth) acrylates include triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and polyethylene glycol (600) di (meth) acrylate. Is exemplified. Further, as a monomer having three (meth) acrylic groups, alkoxylated trimethylolpropane tri (meth) acrylates, glycerol propoxytri (meth) acrylate, pentaerythritol tri (meth) acrylate, and tris (2-hydroxy). Examples thereof include ethyl) isocyanurate tri (meth) acrylate. Examples of the alkoxylated trimethylolpropane tri (meth) acrylate include trimethylolpropane tri (meth) acrylate and trimethylolpropane triethoxytri (meth) acrylate. Further, examples of the monomer having four (meth) acrylic groups include pentaerythritol tetra (meth) acrylate and ditrimethylolpropane tetra (meth) acrylate. Further, as a monomer having five (meth) acrylic groups, dipentaerythritol penta (meth) acrylate and the like are exemplified. Further, as a monomer having 6 (meth) acrylic groups, ditrimethylolpropane hexa (meth) acrylate and the like are exemplified. Examples of the polyfunctional monomer also include diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene and the like.

Examples of the mercapto group-containing compound include alkyl group-substituted mercaptans, allyl group-substituted mercaptans, aryl group-substituted mercaptans, hydroxy group-substituted mercaptans, alkoxy group-substituted mercaptans, cyano group-substituted mercaptans, amino group-substituted mercaptans, silyl group-substituted mercaptans, and acid group-substituted mercaptans. Examples thereof include mercaptans, halo group-substituted mercaptans, and acyl group-substituted mercaptans. As the alkyl group-substituted mercaptan, an alkyl group-substituted mercaptan having 1 to 20 carbon atoms is preferable, and an alkyl group-substituted mercaptan having 1 to 10 carbon atoms is more preferable. As the aryl group-substituted mercaptan, a phenyl group-substituted mercaptan is preferable. As the alkoxy group-substituted mercaptan, an alkoxy group-substituted mercaptan having 1 to 20 carbon atoms is preferable, and an alkoxy group-substituted mercaptan having 1 to 10 carbon atoms is more preferable. The acid group-substituted mercaptan is preferably an alkyl group-substituted mercaptan having a carboxyl group and having 1 to 10 carbon atoms, or an aryl group-substituted mercaptan having a carboxyl group and having 1 to 12 carbon atoms.

(Glass transition temperature of elastic body)
Since a cured product or molded product having excellent toughness can be obtained, the glass transition temperature of the elastic body (hereinafter, may be simply referred to as “Tg”) is preferably 80 ° C. or lower, more preferably 70 ° C. or lower. 60 ° C or lower is more preferable, 50 ° C or lower is more preferable, 40 ° C or lower is more preferable, 30 ° C or lower is more preferable, 20 ° C or lower is more preferable, 10 ° C or lower is more preferable, 0 ° C or lower is more preferable, and − 20 ° C or lower is more preferable, −40 ° C or lower is more preferable, −45 ° C or lower is more preferable, −50 ° C or lower is more preferable, −55 ° C or lower is more preferable, −60 ° C or lower is more preferable, and −65 ° C. The following is more preferable, −70 ° C. or lower is more preferable, −75 ° C. or lower is more preferable, −80 ° C. or lower is more preferable, −85 ° C. or lower is more preferable, −90 ° C. or lower is more preferable, and −95 ° C. or lower is more preferable. More preferably, -100 ° C or lower is more preferable, -105 ° C or lower is more preferable, -110 ° C or lower is more preferable, -115 ° C or lower is more preferable, -120 ° C or lower is further preferable, and -125 ° C or lower is particularly preferable. .. According to this composition, granules having a low Tg can be obtained. As a result, the resulting resin composition containing granules can provide a cured product or a molded product having excellent toughness.

On the other hand, since it is possible to suppress a decrease in the elastic modulus (rigidity) of the obtained cured product or molded product, that is, a cured product or molded product having a sufficient elastic modulus (rigidity) can be obtained, the Tg of the elastic body is , 0 ° C. or higher, more preferably 20 ° C. or higher, further preferably 50 ° C. or higher, particularly preferably 80 ° C. or higher, and most preferably 120 ° C. or higher.

The Tg of the elastic body can be determined by the composition of the structural unit contained in the elastic body and the like. In other words, the Tg of the obtained elastic body can be adjusted by changing the composition of the monomer used when producing (polymerizing) the elastic body.

The Tg of the elastic body can be obtained by performing viscoelasticity measurement using a flat plate made of the elastic body. Specifically, Tg can be measured as follows: (1) For a flat plate made of an elastic body, a dynamic viscoelasticity measuring device (for example, DVA-200 manufactured by IT Measurement Control Co., Ltd.) is used. , Dynamic viscoelasticity measurement is performed under tensile conditions to obtain a graph of tan δ; (2) With respect to the obtained graph of tan δ, the peak temperature of tan δ is defined as the glass transition temperature. Here, in the graph of tan δ, when a plurality of peaks are obtained, the lowest peak temperature is set as the glass transition temperature of the elastic body.

Here, when a homopolymer obtained by polymerizing only one type of monomer is obtained, a group of monomers that provide a homopolymer having a Tg larger than 0 ° C. is referred to as a monomer group a. .. Further, when a homopolymer obtained by polymerizing only one type of monomer is obtained, a group of monomers that provide a homopolymer having a Tg of less than 0 ° C. is referred to as a monomer group b. The structural unit derived from at least one monomer selected from the monomer group a is 50 to 100% by weight (more preferably 65 to 99% by weight), and at least selected from the monomer group b. An elastic body containing 0 to 50% by weight (more preferably 1 to 35% by weight) of a structural unit derived from one kind of monomer is referred to as an elastic body X. The elastic body X has a Tg larger than 0 ° C. Further, when the elastic body contains the elastic body X, the resin composition containing the obtained granules can provide a cured product or a molded product having sufficient rigidity.

Even when the Tg of the elastic body is larger than 0 ° C., it is preferable that the crosslinked structure is introduced into the elastic body. Examples of the method for introducing the crosslinked structure include the above methods.

The monomer that can be contained in the monomer group a is not limited to the following, but for example, unsubstituted vinyl aromatic compounds such as styrene and 2-vinylnaphthalene; and vinyl substitution such as α-methylstyrene. Aromatic compounds; ring-alkylated vinyls such as 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,5-dimethylstyrene, 2,4,6-trimethylstyrene Aromatic compounds; Ring-alkenylated vinyl aromatic compounds such as 4-methoxystyrene and 4-ethoxystyrene; Ring-halogenated vinyl aromatic compounds such as 2-chlorostyrene and 3-chlorostyrene; 4-Acetoxystyrene and the like. Ring ester-substituted vinyl aromatic compounds; Ring hydroxylated vinyl aromatic compounds such as 4-human oxystyrene; Vinyl esters such as vinyl benzoate and vinyl cyclohexanoate; Vinyl halides such as vinyl chloride; , Aromatic monomers such as inden; Alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate; Aromatic methacrylates such as phenyl methacrylate; Methacrylates such as isobornyl methacrylate and trimethylsilyl methacrylate; Examples thereof include methacrylic monomers containing a methacrylic acid derivative; certain acrylic acid esters such as isobornyl acrylate and tert-butyl acrylate; and acrylic monomers containing an acrylic acid derivative such as acrylonitrile. Further, as the monomers that can be contained in the monomer group a, acrylamide, isopropylacrylamide, N-vinylpyrrolidone, isobornyl methacrylate, dicyclopentanyl methacrylate, 2-methyl-2-adamantyl methacrylate, 1- Examples thereof include monomers such as adamantyl acrylate and 1-adamantyl methacrylate, which can provide a homopolymer having a Tg of 120 ° C. or higher when used as a homopolymer. Only one kind of these monomers a may be used, or two or more kinds thereof may be used in combination.

Examples of the monomer b include ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, 2-hydroxyethyl acrylate, and 4-hydroxybutyl acrylate. Only one kind of these monomers b may be used, or two or more kinds may be used in combination. Among these monomers b, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate are particularly preferable.

(Volume average particle size of elastic body)
The volume average particle size of the elastic body is preferably 0.03 μm to 50.00 μm, more preferably 0.05 μm to 10.00 μm, more preferably 0.08 μm to 2.00 μm, still more preferably 0.10 μm to 1.00 μm. , 0.10 μm to 0.80 μm is even more preferable, and 0.10 μm to 0.50 μm is particularly preferable. When the volume average particle size of the elastic body is (a) 0.03 μm or more, an elastic body having a desired volume average particle size can be stably obtained, and when (b) 50.00 μm or less, it can be obtained. The heat resistance and impact resistance of the cured product or molded product are improved. The volume average particle size of the elastic body can be measured by using an aqueous latex containing the elastic body as a sample and using a dynamic light scattering type particle size distribution measuring device or the like. The volume average particle size of the elastic body will be described in detail in the following examples.

(Ratio of elastic body)
The proportion of the elastic body in the polymer fine particles (A) is preferably 40 to 97% by weight, more preferably 60 to 95% by weight, and 70 to 93% by weight, assuming that the entire polymer fine particles (A) are 100% by weight. Is even more preferable. When the ratio of the elastic body is (a) 40% by weight or more, the obtained resin composition containing granules can provide a cured product or a molded product having excellent toughness and impact resistance, and (b). When it is 97% by weight or less, the polymer fine particles (A) do not easily aggregate, so that the resin composition containing the obtained granules does not have a high viscosity, and as a result, the resin composition is excellent in handling. It can be a plastic.

(Gel content of elastic body)
The elastic body is preferably one that can swell in a suitable solvent but is substantially insoluble. The elastic body is preferably unnecessary with respect to the thermosetting resin or thermoplastic resin used.

The elastic body preferably has a gel content of 60% by weight or more, more preferably 80% by weight or more, further preferably 90% by weight or more, and particularly preferably 95% by weight or more. When the gel content of the elastic body is within the above range, the resin composition containing the obtained granules can provide a cured product or a molded product having excellent toughness.

In the present specification, the method for calculating the gel content is as follows. First, an aqueous latex containing the polymer fine particles (A) is obtained, and then a powder or granular material of the polymer fine particles (A) is obtained from the aqueous latex. The method for obtaining the powder or granular material of the polymer fine particles (A) from the aqueous latex is not particularly limited, but for example, (i) the polymer fine particles (A) in the aqueous latex are aggregated, and (ii) the obtained aggregation is obtained. Examples thereof include a method of obtaining a powder or granular material of the polymer fine particles (A) by dehydrating the product and (iii) further drying the agglomerate. Next, 2.0 g of the polymer fine particles (A) are dissolved in 50 mL of methyl ethyl ketone. Then, the obtained MEK lysate is separated into a MEK-soluble component (MEK-soluble component) and a MEK-insoluble component (MEK-insoluble component). Specifically, using a centrifuge (CP60E manufactured by Hitachi Koki Co., Ltd.), the obtained MEK lysate is subjected to centrifugation at a rotation speed of 30,000 rpm for 1 hour, and the lysate can be used for MEK. It separates into a dissolved component and a MEK insoluble component. Here, a total of three sets of centrifugation operations are performed. The weights of the obtained MEK soluble and MEK insoluble components are measured, and the gel content is calculated from the following formula.
Gel content (%) = (weight of methyl ethyl ketone insoluble content) / {(weight of methyl ethyl ketone insoluble content) + (weight of methyl ethyl ketone soluble content)} x 100.

(Modification example of elastic body)
In one embodiment of the present invention, the elastic body is one selected from the group consisting of a diene-based rubber, a (meth) acrylate-based rubber, and a polysiloxane rubber-based elastic body, and has a structural unit having the same composition. It may consist of only one type of elastic body. In one embodiment of the present invention, the elastic body may consist of a plurality of types of elastic bodies, each having a structural unit having a different composition.

In one embodiment of the present invention, a case where the elastic body is composed of a plurality of types of elastic bodies will be described. In this case, each of the plurality of types of elastic bodies is referred to as elastic body ₁ , elastic body ₂ , ..., And elastic body _n . Here, n is an integer of 2 or more. The elastic body may contain a mixture obtained by mixing _{the elastic body 1} , the elastic body ₂ , ..., And the elastic body _n , which are separately polymerized. The elastic body may contain a polymer obtained by multi-stage polymerization of the elastic body ₁ , the elastic body ₂ , ..., And the elastic body _n. A polymer obtained by multi-stage polymerization of a plurality of types of elastic bodies is also referred to as a multi-stage polymerization elastic body. The method for producing the multi-stage polymerized elastic body will be described in detail later.

A multi-stage polymerized elastic body composed of elastic body ₁ , elastic body ₂ , ..., And elastic body _{n will be described.} In the multi-stage polymer elastic body, the elastic body _n may or may cover at least a portion of the elastic body _n-1, or the whole of the elastic body _n-1 coating. In the multi-stage polymer elastic body, sometimes some of the elastic body _n has entered the inside of the elastic body _n-1.

In the multi-stage polymerized elastic body, each of the plurality of elastic bodies may have a layered structure. For example, when the multi-stage polymerized elastic body is _{composed of the elastic body 1} , the elastic body ₂ , and the elastic body ₃ , the elastic body ₁ is the innermost layer, the layer _{of the elastic body 2} exists on the outside of the elastic body ₁ , and the elastic body is further formed. An embodiment in which the layer of the elastic body _{3 exists as the outermost layer in the elastic body outside the layer 2} is also an aspect of the present invention. As described above, a multi-stage polymerized elastic body in which each of the plurality of elastic bodies has a layered structure can be said to be a multi-layer elastic body. That is, in one embodiment of the present invention, the elastic body may include a mixture of a plurality of types of elastic bodies, a multi-stage polymerized elastic body and / or a multilayer elastic body.

(2-3-2. Graft part)
In the present specification, a polymer graft-bonded to an elastic body is referred to as a graft portion. The graft portion contains, as a structural unit, a structural unit derived from one or more kinds of monomers selected from the group consisting of an aromatic vinyl monomer, a vinyl cyan monomer, and a (meth) acrylate monomer. It is preferably a polymer. The graft portion having this structure can play various roles. The "various roles" are, for example, (a) improving the compatibility between the polymer fine particles (A) and the thermosetting resin or the thermoplastic resin, and (b) the matrix resin (C) to be mixed. To improve the dispersibility of the polymer fine particles (A) in the thermosetting resin or the thermoplastic resin, and (c) the polymer fine particles (A) in the resin composition containing the obtained granules or the cured product or molded product thereof. Is dispersed in the state of primary particles, and so on.

Specific examples of the aromatic vinyl monomer include styrene, α-methylstyrene, p-methylstyrene, divinylbenzene and the like.

Specific examples of the vinyl cyan monomer include acrylonitrile and methacrylonitrile.

Specific examples of the (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hydroxyethyl (meth) acrylate, and hydroxybutyl (meth) acrylate. As used herein, (meth) acrylate means acrylate and / or methacrylate.

As the above-mentioned one or more kinds of monomers selected from the group consisting of aromatic vinyl monomer, vinyl cyanone monomer, and (meth) acrylate monomer, only one kind may be used. Two or more types may be used in combination.

The graft portion preferably contains a structural unit derived from a reactive group-containing monomer as a structural unit. The reactive group-containing monomer is composed of an epoxy group, an oxetane group, a hydroxyl group, an amino group, an imide group, a carboxylic acid group, a carboxylic acid anhydride group, a cyclic ester, a cyclic amide, a benzoxazine group, and a cyanate ester group. It is preferable that the monomer contains one or more reactive groups selected from the group consisting of, and contains one or more reactive groups selected from the group consisting of an epoxy group, a hydroxyl group, and a carboxylic acid group. It is more preferable that it is a monomer. According to the above structure, the graft portion of the polymer fine particles (A) and the thermosetting resin or the thermoplastic resin can be chemically bonded in the obtained resin composition containing the granules. Thereby, in the resin composition containing the obtained granules, in the cured product thereof, or in the molded product, the polymer fine particles (A) are maintained in a good dispersed state without aggregating the polymer fine particles (A). Can be done.

Specific examples of the monomer having an epoxy group include glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and allyl glycidyl ether.

Specific examples of the monomer having a hydroxyl group include hydroxy linear alkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate (particularly). , Hydroxy linear C1-6 alkyl (meth) acrylate); Caprolactone-modified hydroxy (meth) acrylate; Hydroxy branched alkyl (meth) acrylate such as methyl α- (hydroxymethyl) acrylate, ethyl α- (hydroxymethyl) acrylate) Hydroxy group-containing (meth) acrylates such as mono (meth) acrylates of polyester diols (particularly saturated polyester diols) obtained from divalent carboxylic acids (phthalic acid, etc.) and dihydric alcohols (propylene glycol, etc.) Can be mentioned.

Specific examples of the monomer having a carboxylic acid group include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid, and dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid. As the monomer having a carboxylic acid group, the monocarboxylic acid is preferably used.

Only one type of the above-mentioned reactive group-containing monomer may be used, or two or more types may be used in combination.

The graft portion preferably contains 0.5 to 90% by weight, more preferably 1 to 50% by weight, and 2 to 50% by weight of the structural unit derived from the reactive group-containing monomer in 100% by weight of the graft portion. It is more preferably contained in an amount of 35% by weight, and particularly preferably contained in an amount of 3 to 20% by weight. When the graft portion contains (a) 0.5% by weight or more of the structural unit derived from the reactive group-containing monomer in 100% by weight of the graft portion, the resin composition containing the obtained granules has sufficient resistance. A cured product or molded product having impact resistance can be provided, and (b) when 90% by weight or less is contained, the obtained resin composition containing granules provides a cured product or molded product having sufficient impact resistance. It has the advantage that the storage stability of the resin composition is improved.

The structural unit derived from the reactive group-containing monomer is preferably contained in the graft portion, and more preferably contained only in the graft portion.

The graft portion may contain a structural unit derived from a polyfunctional monomer as a structural unit. When the graft portion contains a structural unit derived from a polyfunctional monomer, (a) the swelling of the polymer fine particles (A) in the resin composition containing the obtained granules can be prevented, (b). Since the viscosity of the resin composition containing the obtained granules is low, the handleability of the resin composition tends to be good, and (c) the polymer fine particles (A) in the thermosetting resin or the thermoplastic resin. It has advantages such as improved dispersibility.

When the graft portion does not contain a structural unit derived from a polyfunctional monomer, the resin composition containing the obtained granules is compared with the case where the graft portion contains a structural unit derived from a polyfunctional monomer. , A cured product or a molded product having better toughness and impact resistance can be provided.

Examples of the polyfunctional monomer that can be used for the polymerization of the graft portion include the same monomers as the above-mentioned polyfunctional monomer. Among these polyfunctional monomers, the polyfunctional monomers that can be preferably used for the polymerization of the graft portion include allyl methacrylate, ethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, and butane diol di. Examples thereof include (meth) acrylate, hexanediol di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, and polyethylene glycol di (meth) acrylate. Only one kind of these polyfunctional monomers may be used, or two or more kinds thereof may be used in combination.

The graft portion preferably contains 1 to 20% by weight, more preferably 5 to 15% by weight, of a structural unit derived from a polyfunctional monomer in 100% by weight of the graft portion.

As the constituent unit, the graft portion may include a constituent unit derived from another monomer in addition to the constituent unit derived from the above-mentioned monomer.

Further, the graft portion is preferably a polymer graft-bonded to an elastic body described later. When the graft portion is a polymer graft-bonded to an elastic body described later, "arbitrary polymer" is replaced with "elastic body" in the following description.

(Glass transition temperature of graft part)
The glass transition temperature of the graft portion (hereinafter, may be simply referred to as “Tg”) is preferably 190 ° C. or lower, more preferably 160 ° C. or lower, more preferably 140 ° C. or lower, more preferably 120 ° C. or lower, and more preferably 80 ° C. The following is preferable, 70 ° C. or lower is more preferable, 60 ° C. or lower is more preferable, 50 ° C. or lower is more preferable, 40 ° C. or lower is more preferable, 30 ° C. or lower is more preferable, 20 ° C. or lower is more preferable, and 10 ° C. or lower is more preferable. More preferably, 0 ° C. or lower is more preferable, −20 ° C. or lower is more preferable, −40 ° C. or lower is more preferable, −45 ° C. or lower is more preferable, −50 ° C. or lower is more preferable, −55 ° C. or lower is more preferable, and −55 ° C. or lower is more preferable. -60 ° C or lower is more preferable, -65 ° C or lower is more preferable, -70 ° C or lower is more preferable, -75 ° C or lower is more preferable, -80 ° C or lower is more preferable, -85 ° C or lower is more preferable, and -90 ° C is more preferable. ° C or lower is more preferable, -95 ° C or lower is more preferable, -100 ° C or lower is more preferable, -105 ° C or lower is more preferable, -110 ° C or lower is more preferable, -115 ° C or lower is more preferable, and -120 ° C or lower. Is more preferable, and −125 ° C. or lower is particularly preferable.

The glass transition temperature of the graft portion is preferably 0 ° C. or higher, more preferably 30 ° C. or higher, more preferably 50 ° C. or higher, further preferably 70 ° C. or higher, further preferably 90 ° C. or higher, and particularly preferably 110 ° C. or lower. preferable.

The Tg of the graft portion can be determined by the composition of the structural unit contained in the graft portion and the like. In other words, the Tg of the obtained graft portion can be adjusted by changing the composition of the monomer used when producing (polymerizing) the graft portion.

The Tg of the graft portion can be obtained by performing viscoelasticity measurement using a flat plate made of polymer fine particles. Specifically, Tg can be measured as follows: (1) For a flat plate made of polymer fine particles, a dynamic viscoelasticity measuring device (for example, DVA-200 manufactured by IT Measurement Control Co., Ltd.) is used. Then, the dynamic viscoelasticity measurement is performed under tensile conditions to obtain a graph of tan δ; (2) With respect to the obtained graph of tan δ, the peak temperature of tan δ is defined as the glass transition temperature. Here, in the graph of tan δ, when a plurality of peaks are obtained, the highest peak temperature is set as the glass transition temperature of the graft portion.

(Graft rate of graft part)
In one embodiment of the present invention, the polymer fine particles (A) may have a polymer having the same composition as the graft portion and may have a polymer that is not graft-bonded to any polymer. .. In the present specification, a polymer having the same structure as the graft portion and not graft-bonded to any polymer is also referred to as a non-grafted polymer. The non-grafted polymer also constitutes a part of the polymer fine particles (A) according to the embodiment of the present invention. It can be said that the non-grafted polymer is not graft-bonded to any polymer among the polymers produced in the polymerization of the graft portion.

In the present specification, among the polymers produced in the polymerization of the graft portion, the ratio of the polymer graft-bonded to any polymer, that is, the graft portion is referred to as the graft ratio. The graft ratio can be said to be a value represented by (weight of graft portion) / {(weight of graft portion) + (weight of non-grafted polymer)} × 100.

The graft ratio of the graft portion is preferably 70% or more, more preferably 80% or more, and further preferably 90% or more. When the graft ratio is 70% or more, there is an advantage that the viscosity of the resin composition containing the obtained granules does not become too high.

In the present specification, the method of calculating the graft ratio is as follows. First, an aqueous latex containing the polymer fine particles (A) is obtained, and then a powder or granular material of the polymer fine particles (A) is obtained from the aqueous latex. As a method for obtaining the powder or granular material of the polymer fine particles (A) from the aqueous latex, specifically, (i) the polymer fine particles (A) in the aqueous latex are aggregated, and (ii) the obtained aggregate is obtained. Examples thereof include a method of obtaining powder or granular material of the polymer fine particles (A) by dehydrating (iii) and further drying the aggregate. Next, 2 g of the polymer fine particles (A) are dissolved in 50 mL of methyl ethyl ketone (hereinafter, also referred to as MEK). Then, the obtained MEK lysate is separated into a MEK-soluble component (MEK-soluble component) and a MEK-insoluble component (MEK-insoluble component). Specifically, using a centrifuge (CP60E manufactured by Hitachi Koki Co., Ltd.), the obtained MEK lysate is subjected to centrifugation at a rotation speed of 30,000 rpm for 1 hour, and the lysate can be used for MEK. It separates into a dissolved component and a MEK insoluble component. Here, a total of three sets of centrifugation operations may be performed. Next, 20 mL of concentrated MEK-soluble matter is added to 200 mL of methanol and mixed. Then, an aqueous calcium chloride solution prepared by dissolving 0.01 g of calcium chloride in water is added to the mixture, and the mixture is stirred for 1 hour. Then, the obtained mixture is separated into a methanol-soluble component and a methanol-insoluble component, and the amount of the methanol-insoluble component is defined as the amount of free polymer (FP amount). Then, the graft ratio can be calculated by the following formula.
Graft rate (%) = 100-[(FP amount) / {(FP amount) + (MEK insoluble matter)}] / (weight of polymer in graft part) x 10000
The weight of the polymer other than the graft portion is the amount of the monomer charged up to the polymer other than the graft portion. The polymer other than the graft portion is an arbitrary polymer (for example, an elastic body). When the polymer fine particles (A) contain a surface crosslinked polymer described later, the polymer other than the graft portion contains, for example, both an elastic polymer and a surface crosslinked polymer. Further, in calculating the graft ratio, the method of aggregating the polymer fine particles (A) is not particularly limited, and a method using a solvent, a method using an aggregating agent (also referred to as a coagulant), a method of spraying an aqueous latex, and the like are used. Can be used. The weight of the polymer in the graft portion is the amount of the monomers constituting the polymer in the graft portion.

(Modification example of graft part)
In one embodiment of the present invention, the graft portion may consist of only one type of graft portion having a structural unit having the same composition. In one embodiment of the present invention, the graft portion may consist of a plurality of types of graft portions, each having a constituent unit having a different composition.

In one embodiment of the present invention, a case where the graft portion is composed of a plurality of types of graft portions will be described. In this case, each of the plurality of types of graft portions is referred to as a graft portion ₁ , a graft portion ₂ , ..., A graft portion _n (n is an integer of 2 or more). The graft portion may contain a mixture obtained by mixing _{the graft portion 1} , the graft portion ₂ , ..., And the graft portion _n, which are polymerized separately, respectively. The graft portion may contain a polymer obtained by sequentially polymerizing _{the graft portion 1} , the graft portion ₂ , ..., And the graft portion _{n, respectively.} Such polymerization of a plurality of polymers (graft portions) in order is also referred to as multistage polymerization. A polymer obtained by multi-stage polymerization of a plurality of types of graft portions is also referred to as a multi-stage polymerization graft portion. The method for producing the multistage polymerization graft portion will be described in detail later.

When the graft portion is composed of a plurality of types of graft portions, all of the plurality of types of graft portions may not be graft-bonded to any polymer. At least a part of at least one graft portion may be graft-bonded to an arbitrary polymer, and the graft portions of other species (several other species) may be graft-bonded to an arbitrary polymer. It may be graft-bonded to the graft portion. When the graft portion is composed of a plurality of types of graft portions, a plurality of types of polymers (plural types) that have the same configuration as the plurality of types of graft portions and are not graft-bonded to any polymer. (Non-graft polymer).

A multi-stage polymerization graft portion including the graft portion ₁ , the graft portion ₂ , ..., And the graft portion _{n will be described.} In the multi-stage polymerization grafts, the graft section _n may either be coated onto at least a portion of the graft portion _n-1, or may cover the entire graft portion _n-1. In the multi-stage polymerization grafting unit, a portion of the graft portion _n sometimes has entered the inside of the graft portion _n-1.

In the multi-stage polymerization graft portion, each of the plurality of graft portions may have a layered structure. For example, when the multi-stage polymerization graft portion is _{composed of the graft portion 1} , the graft portion ₂ , and the graft portion ₃ , the graft portion ₁ is the innermost layer in the graft portion, and the layer of the graft portion ₂ exists _{outside the graft portion 1. Further, an embodiment in which the layer of the graft portion 3} exists as the outermost layer outside the layer of the graft portion ₂ is also an aspect of the present invention. As described above, the multistage polymerization graft portion in which each of the plurality of graft portions has a layered structure can be said to be a multilayer graft portion. That is, in one embodiment of the present invention, the graft portion may include a mixture of a plurality of types of graft portions, a multi-stage polymerization graft portion and / or a multilayer graft portion.

When an arbitrary polymer and a graft portion are polymerized in this order in the production of the polymer fine particles (A), at least a part of the graft portion is at least a part of the arbitrary polymer in the obtained polymer fine particles (A). Can be coated. In other words, it can be said that the arbitrary polymer and the graft portion are polymerized in this order, in other words, the arbitrary polymer and the graft portion are polymerized in multiple stages. The polymer fine particles (A) obtained by multi-stage polymerization of an arbitrary polymer and a graft portion can be said to be a multi-stage polymer.

When the polymer fine particles (A) are multi-stage polymers, the graft portion can cover at least a part of any polymer or the whole of any polymer. When the polymer fine particles (A) are multi-stage polymers, a part of the graft portion may enter the inside of an arbitrary polymer.

When the polymer fine particles (A) are multi-stage polymers, any polymer and graft portion may have a layered structure. For example, an embodiment in which an arbitrary polymer is an innermost layer (also referred to as a core layer) and a layer of a graft portion is present as an outermost layer (also referred to as a shell layer) outside the arbitrary polymer is also an aspect of the present invention. Is. A structure in which an arbitrary polymer is used as a core layer and a graft portion is used as a shell layer can be said to be a core-shell structure. As described above, the polymer fine particles (A) in which any polymer and the graft portion have a layered structure (core-shell structure) can be said to be a multilayer polymer or a core-shell polymer. That is, in one embodiment of the present invention, the polymer fine particles (A) may be a multi-stage polymer and / or a multilayer polymer or a core-shell polymer. However, as long as the polymer fine particles (A) have a graft portion, the polymer fine particles (A) are not limited to the above-mentioned constitution.

It is preferred that at least a portion of the graft portion covers at least a portion of any polymer. In other words, it is preferable that at least a part of the graft portion is present on the outermost side of the polymer fine particles (A).

(2-3-3. Surface crosslinked polymer)
It is preferable that the polymer fine particles (A) further have a surface crosslinked polymer in addition to the elastic body and the graft portion graft-bonded to the elastic body. Hereinafter, the surface crosslinked polymer will be described by taking as an example the case where the polymer fine particles (A) further have a surface crosslinked polymer in addition to the elastic body and the graft portion. According to the above configuration, in the production of (a) polymer fine particles (A), blocking resistance can be improved, and (b) the weight in the matrix resin (C) in the obtained resin composition containing granules. The dispersibility of the coalesced fine particles (A) becomes better. These reasons are not particularly limited, but can be presumed as follows: The surface crosslinked polymer exposes the elastic portion of the polymer fine particles (A), for example, by coating at least a part of the elastic body. As a result, the elastic bodies are less likely to stick to each other, so that the dispersibility of the polymer fine particles (A) is improved.

When the polymer fine particles (A) have a surface crosslinked polymer, they may also have the following effects: (a) the effect of reducing the viscosity of the resin composition containing the obtained granules, (b) the crosslink density in the elastic body. The effect of increasing, and (c) the effect of increasing the graft efficiency of the graft portion. The crosslink density in an elastic body means the degree of the number of crosslinked structures in the entire elastic body.

As the structural unit of the surface crosslinked polymer, 30 to 100% by weight of the structural unit derived from the polyfunctional monomer and 0 to 70% by weight of the structural unit derived from other vinyl-based monomers, totaling 100. It consists of a polymer containing% by weight.

Examples of the polyfunctional monomer that can be used for the polymerization of the surface crosslinked polymer include the same monomers as the above-mentioned polyfunctional monomer. Among these polyfunctional monomers, the polyfunctional monomers that can be preferably used for the polymerization of surface crosslinked polymers include allyl methacrylate, ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, and hexane. Examples thereof include diol di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, and polyethylene glycol di (meth) acrylate. Only one kind of these polyfunctional monomers may be used, or two or more kinds thereof may be used in combination.

The polymer fine particles (A) may contain a surface crosslinked polymer that is polymerized independently of the polymerization of the rubber-containing graft copolymer, or the surface crosslinked weight polymerized together with the rubber-containing graft copolymer. May include coalescence. The polymer fine particles (A) may be a multi-stage polymer obtained by multi-stage polymerization of an elastic body, a surface crosslinked polymer, and a graft portion in this order. In any of these embodiments, the surface crosslinked polymer may cover at least a portion of the elastic body.

The surface crosslinked polymer can also be considered as part of the elastic body. In other words, the surface crosslinked polymer can be regarded as a part of the rubber-containing graft copolymer, and can be said to be a surface crosslinked polymer. When the polymer fine particles (A) contain a surface crosslinked polymer, the graft portion may be graft-bonded to an elastic material other than (a) the surface crosslinked polymer, and may be graft-bonded to (b) the surface crosslinked polymer. It may be graft-bonded to both an elastic body other than the (c) surface-crosslinked polymer and a surface-crosslinked polymer. When the polymer fine particles (A) contain a surface crosslinked polymer, the volume average particle size of the elastic body described above is intended to be the volume average particle size of the elastic body containing the surface crosslinked polymer.

A case (case D) in which the polymer fine particles (A) are a multi-stage polymer obtained by multi-stage polymerization of an elastic body, a surface crosslinked polymer, and a graft portion in this order will be described. In Case D, the surface crosslinked polymer may cover part of the elastic or the entire elastic. In case D, a part of the surface crosslinked polymer may have entered the inside of the elastic body. In case D, the graft portion can cover a part of the surface crosslinked polymer or can cover the whole surface crosslinked polymer. In case D, a part of the graft portion may enter the inside of the surface crosslinked polymer. In Case D, the elastic body, the surface crosslinked polymer and the graft portion may have a layered structure. For example, the elastic body is the innermost layer (core layer), the surface crosslinked polymer layer is present as an intermediate layer on the outside of the elastic body, and the grafted layer is the outermost layer (shell layer) on the outside of the surface crosslinked polymer. The existing aspect is also one aspect of the present invention.

(2-3-4. Volume average particle size (Mv) of polymer fine particles (A))
The volume average particle diameter (Mv) of the polymer fine particles (A) is preferably 0.03 μm to 50.00 μm because the resin composition containing the obtained granules has a desired viscosity and is highly stable. , 0.05 μm to 10.00 μm, more preferably 0.08 μm to 2.00 μm, further preferably 0.10 μm to 1.00 μm, even more preferably 0.10 μm to 0.80 μm, 0.10 μm to 0.10 μm. 0.50 μm is particularly preferable. The volume average particle diameter (Mv) of the polymer fine particles (A) is 0.1 to 0.5 μm because the dispersibility of the polymer fine particles (A) in the thermosetting resin or the thermoplastic resin is good. Is even more preferable. In the present specification, the "volume average particle size (Mv) of the polymer fine particles (A)" is intended to mean the volume average particle size of the primary particles of the polymer fine particles (A) unless otherwise specified. do. The volume average particle size of the polymer fine particles (A) can be measured by using an aqueous latex containing the polymer fine particles (A) as a sample and using a dynamic light scattering type particle size distribution measuring device or the like. The volume average particle size of the polymer fine particles (A) will be described in detail in the following Examples. For the volume average particle size of the polymer fine particles (A), the cured product of the resin composition containing the obtained granules is cut, and the cut surface is imaged using an electron microscope or the like, and the obtained imaged data (image image) is obtained. It can also be measured using.

The number distribution of the particle size of the polymer fine particles (A) in the thermosetting resin or the thermoplastic resin is 0 because the resin composition containing the obtained granules has a low viscosity and is easy to handle. It is preferable to have a half price range of .5 times or more and 1 times or less.

(2-3-5. Method for producing polymer fine particles (A) (latex production process))
In one embodiment of the present invention, the powder / granule preparation step is, for example, a step of producing polymer fine particles (A), particularly a latex production step of producing a latex containing the polymer fine particles (A), before the slurry preparation step. May include. Latex is intended to be water-based latex.

The polymer fine particles (A) can be produced, for example, by polymerizing an elastic body and then graft-polymerizing a polymer constituting a graft portion with respect to the elastic body in the presence of the elastic body.

The polymer fine particles (A) can be produced by a known method, for example, a method such as emulsion polymerization, suspension polymerization, or microsuspension polymerization. Specifically, the polymerization of the elastic body in the polymer fine particles (A), the polymerization of the graft portion (graft polymerization), and the polymerization of the surface crosslinked polymer are known methods, for example, emulsion polymerization, suspension polymerization, microsuspension polymerization. It can be manufactured by a method such as. Among these, the aqueous latex of the polymer fine particles (A), which is easy to design the composition of the polymer fine particles (A), is easy to industrially produce, and can be suitably used for producing granules, can be easily obtained. Therefore, emulsion polymerization is preferable as a method for producing the polymer fine particles (A). Hereinafter, a method for producing an elastic body, a graft portion, and a surface crosslinked polymer having an arbitrary configuration, which can be contained in the polymer fine particles (A), will be described.

(Manufacturing method of elastic body)
Consider the case where the elastic body contains at least one selected from the group consisting of a diene-based rubber and a (meth) acrylate-based rubber. In this case, the elastic body can be produced by, for example, emulsion polymerization, suspension polymerization, microsuspension polymerization, or the like, and as the production method, for example, the method described in WO2005 / 028546 can be used. ..

Consider the case where the elastic body includes a polysiloxane rubber-based elastic body. In this case, the elastic body can be produced by, for example, emulsion polymerization, suspension polymerization, microsuspension polymerization, or the like, and as the production method, for example, the method described in WO2006 / 070664 can be used. ..

A method for manufacturing an elastic body will be described when the elastic body is composed of a plurality of types of elastic bodies (for example, elastic body ₁ , elastic body ₂ , ..., Elastic body _n). In this case, the elastic body ₁ , the elastic body ₂ , ..., The elastic body _n are separately polymerized by the above-mentioned method and then mixed to produce an elastic body having a plurality of types of elastic bodies. May be good. Alternatively, the elastic body ₁ , the elastic body ₂ , ..., And the elastic body _n may be polymerized in multiple stages in this order to produce an elastic body having a plurality of types of elastic bodies.

The multi-stage polymerization of an elastic body will be specifically described. For example, (1) as an elastic body ₁ by polymerizing the elastic member _1; (2) then obtain an elastic body ₂ polymerized by a two-stage elastic member _{1 + 2} in the presence of the elastic member _1; (3) then elastically body _{1 +} obtain ₂ in the presence of the elastic body ₃ polymerized to a three-stage elastic member _{1 + 2 + 3;} (4) below, after the same manner, in the presence of ₊ elastic body _{1 + 2 + · · · (n-1)} The elastic body _n is polymerized to obtain a multi-stage polymerized elastic body _{1 + 2 + ... + N.}

(Manufacturing method of graft part)
The graft portion can be formed, for example, by polymerizing the monomer used for forming the graft portion by a known radical polymerization. When (a) an elastic body or (b) a polymer fine particle precursor containing an elastic body and a surface crosslinked polymer is obtained as an aqueous latex, the polymerization of the graft portion is preferably carried out by an emulsion polymerization method. The graft portion can be manufactured, for example, according to the method described in WO2005 / 028546.

A method for manufacturing the graft portion will be described when the graft portion is composed of a plurality of types of graft portions (for example, the graft portion ₁ , the graft portion ₂ , ..., The graft portion _n). In this case, the graft portion ₁ , the graft portion ₂ , ..., And the graft portion _n are separately polymerized by the above-mentioned method and then mixed to produce a graft portion having a plurality of types of graft portions. May be good. Alternatively, the graft portion ₁ , the graft portion ₂ , ..., And the graft portion _n may be polymerized in multiple stages in this order to produce a graft portion having a plurality of types of graft portions.

The multi-stage polymerization of the graft portion will be specifically described. For example, (1) obtaining a graft portion ₁ by polymerizing a graft portion _1; (2) then obtain grafts ₂ polymerized by two-stage graft section _{1 + 2} in the presence of the graft portion _1; (3) then grafted In the presence of _{part 1 + 2, the graft part 3} is polymerized to obtain a three-stage graft part _{1 + 2 + 3} ; (4) The following is performed in the same manner, and then in the presence of _{the graft part 1 + 2 + ... + (n-1).} The graft portion _n is polymerized to obtain a multi-stage polymerization graft portion _{1 + 2 + ... + N.}

When the graft portion is composed of a plurality of types of graft portions, the polymer fine particles (A) may be produced by polymerizing the graft portions having the plurality of types of graft portions and then graft-polymerizing the graft portions onto an elastic body. .. In the presence of an elastic body, a plurality of types of polymers constituting a plurality of types of graft portions may be sequentially graft-polymerized with respect to the elastic body to produce polymer fine particles (A).

(Method for producing surface crosslinked polymer)
The surface crosslinked polymer can be formed by polymerizing a monomer used for forming the surface crosslinked polymer by a known radical polymerization. When the elastic body is obtained as an aqueous latex, the surface crosslinked polymer is preferably polymerized by an emulsion polymerization method.

When the emulsion polymerization method is adopted as the method for producing the polymer fine particles (A), a known emulsifier (dispersant) can be used for the production of the polymer fine particles (A).

Examples of the emulsifier include (a) an anionic emulsifier such as an acid as exemplified below, an alkali metal salt of the acid, or an ammonium salt of the acid, and (b) a nonionic emulsifier such as an alkyl or aryl-substituted polyethylene glycol. (C) Examples thereof include polyvinyl alcohol, alkyl-substituted cellulose, polyvinylpyrrolidone, and polyacrylic acid derivatives. Examples of the acids include alkyl or aryl sulfonic acid represented by (a1) dioctyl sulfosuccinic acid and dodecylbenzene sulfonic acid, alkyl or aryl ether sulfonic acid, alkyl or aryl sulfuric acid represented by (a2) dodecyl sulfuric acid, or Alkyl or aryl ether sulfate, (a3) alkyl or aryl substituted phosphoric acid, or alkyl or aryl ether substituted phosphoric acid, N-alkyl or aryl sarcosic acid typified by (a4) dodecyl sarcosinic acid, (a5) oleic acid. And alkyl or arylcarboxylic acids typified by stearic acids, alkyl or aryl ether carboxylic acids, and the like. Here, the anionic emulsifier formed from the acids described in (a1) and (a2) is referred to as a sulfur-based emulsifier, and the anionic emulsifier formed from the acids described in (a3) is referred to as a phosphorus-based emulsifier. The anionic emulsifier formed from the acids described in (a4) is referred to as a sarcosic acid-based emulsifier, and the anionic emulsifier formed from the acids described in (a5) is referred to as a carboxylic acid-based emulsifier. Only one type of these emulsifiers may be used, or two or more types may be used in combination.

When the emulsion polymerization method is adopted as the method for producing the polymer fine particles (A), a thermal decomposition type initiator can be used for the production of the polymer fine particles (A). Examples of the pyrolytic initiator include known initiators such as 2,2'-azobisisobutyronitrile, hydrogen peroxide, potassium persulfate, and ammonium persulfate.

A redox-type initiator can also be used in the production of the polymer fine particles (A). The redox-type initiators are (a) peroxides such as organic peroxides and inorganic peroxides, (b) reducing agents such as sodium formaldehyde sulfoxylate and glucose as required, and optionally. It is an initiator in which a transition metal salt such as iron (II) sulfate, a chelating agent such as disodium ethylenediamine tetraacetate, if necessary, and a phosphorus-containing compound such as sodium pyrophosphate, if necessary, are used in combination. Examples of the organic peroxide include t-butyl peroxyisopropyl carbonate, paramentan hydroperoxide, cumene hydroperoxide, dicumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, and t-. Hexyl peroxide and the like can be mentioned. Examples of the inorganic peroxide include hydrogen peroxide, potassium persulfate, and ammonium persulfate.

When a redox-type initiator is used, the polymerization can be carried out even at a low temperature at which the peroxide is substantially not thermally decomposed, and the polymerization temperature can be set in a wide range. Therefore, it is preferable to use a redox-type initiator. Among the redox-type initiators, it is preferable to use organic peroxides such as cumene hydroperoxide, dicumyl peroxide, paramentan hydroperoxide, and t-butyl hydroperoxide as the redox-type initiator. The amount of the initiator used, and when the redox-type initiator is used, the amount of the reducing agent, transition metal salt, chelating agent, and the like used can be used within a known range.

Known chain transfer agents are known when polyfunctional monomers are used to polymerize elastics, grafts or surface crosslinked polymers for the purpose of introducing crosslinked structures into elastics, grafts or surface crosslinked polymers. It can be used within the range of the amount used. By using a chain transfer agent, the molecular weight and / or degree of cross-linking of the obtained elastic body, graft portion or surface cross-linked polymer can be easily adjusted.

In addition to the above-mentioned components, a surfactant can be further used in the production of the polymer fine particles (A). The types and amounts of the surfactants used are in the known range.

In the production of the polymer fine particles (A), conditions such as polymerization temperature, pressure, and deoxidation in the polymerization can be applied within a known range.

(2-4. Resin (B))
In this production method, the resin (B) may be used, and the obtained granules may further contain the resin (B). The resin (B) may be the same type of resin as the matrix resin (C) that can be mixed with the granules, or may be a resin of a different type from the matrix resin (C). As an example, consider a case where the resin (B) is used in the present production method, and the obtained granules are mixed with a matrix resin (C) of the same type as the resin (B) to obtain a resin composition. In this case, it is not possible to distinguish between the resin (B) and the matrix resin (C) in the obtained resin composition. Therefore, apparently, the obtained resin composition seems to have only the matrix resin (C) in addition to the polymer fine particles (A). Next, consider a case where the resin (B) is used in the method for producing the resin composition, and the obtained granules are mixed with a matrix resin (C) of a different type from the resin (B) to obtain a resin composition. In this case, in the obtained resin composition, the resin (B) and the matrix resin (C) can be distinguished. In this case, the finally obtained resin composition may contain the resin (B) as a resin other than the matrix resin (C) in addition to the polymer fine particles (A).

The resin (B) may be, for example, a thermosetting resin, a thermoplastic resin, or any combination of the thermosetting resin and the thermoplastic resin. When the present granules contain the resin (B), the resin (B) may have an effect of enhancing the dispersibility of the polymer fine particles (A) in the resin composition containing the obtained granules.

Examples of the thermosetting resin in the resin (B) include various thermosetting resins described in the section of the matrix resin (C) described later. In the resin (B), only one type of thermosetting resin may be used, or two or more types may be used in combination.

Examples of the thermoplastic resin in the resin (B) include various thermoplastic resins described in the section of the matrix resin (C) described later. In the resin (B), only one type of thermoplastic resin may be used, or two or more types may be used in combination.

The resin (B) is preferably of the same type as the matrix resin (C) because there is no risk of affecting various physical properties of the resin composition or cured product containing the obtained granules or the molded product. That is, when the matrix resin (C) is an epoxy resin, it is preferable that the resin (B) is also an epoxy resin. When the resin (B) is of a different type from the matrix resin (C), it is preferable that the resin (B) is compatible with the matrix resin (C).

(Physical characteristics of resin (B))
The properties of the resin (B) are not particularly limited. The resin (B) is preferably a liquid, a semi-solid, or a solid having a viscosity of 100 mPa · s to 1,000,000 mPa · s at 25 ° C. In addition, "the resin (B) has a viscosity of 100 mPa · s to 1,000,000 mPa · s at 25 ° C." means that "the resin (B) at 25 ° C. has a viscosity of 100 mPa · s to 1,000, It is intended to have a viscosity of 000 mPa · s.

When the resin (B) is a liquid, it is possible to further prevent fusion of the polymer fine particles (A) in the granules and the resin composition by allowing the resin (B) to enter the polymer fine particles (A). It has the advantage of being able to. When the resin (B) is a semi-solid or a solid, the obtained resin composition containing the granules has an advantage that it is less sticky and easy to handle.

The viscosity of the resin (B) can be measured with a viscometer. The method for measuring the viscosity of the resin (B) will be described in detail in the following examples.

Further, the resin (B) is preferably a resin having a differential thermal scanning calorimetry (DSC) thermogram having an endothermic peak of 25 ° C. or lower, and more preferably a resin having an endothermic peak of 0 ° C. or lower.

When the resin (B) is used in this production method, the mixing ratio of the polymer fine particles (A) and the resin (B) is 100% by weight based on the total of the polymer fine particles (A) and the resin (B). In some cases, the polymer fine particles (A) are preferably 50 to 99% by weight, and the resin (B) is preferably 1 to 50% by weight. Further, from the viewpoint of blocking resistance, the polymer fine particles (A) are more preferably 70 to 99% by weight, the resin (B) is 1 to 30% by weight, and more preferably the polymer fine particles (A) are 80 to 80% by weight. 99% by weight, the resin (B) is 1 to 20% by weight, particularly preferably the polymer fine particles (A) are 90 to 99% by weight, and the resin (B) is 1 to 10% by weight, most preferably the weight. The combined fine particles (A) are 95 to 99% by weight, and the resin (B) is 1 to 5% by weight.

Further, from the viewpoint of the dispersibility of the polymer fine particles (A) with respect to the matrix resin (C) (hereinafter, also simply referred to as “dispersibility”), the mixing ratio of the polymer fine particles (A) and the resin (B) is heavy. When the total of the coalesced fine particles (A) and the resin (B) is 100% by weight, the polymer fine particles (A) are preferably 60 to 95% by weight, and the resin (B) is 5 to 40% by weight. More preferably, the polymer fine particles (A) are 60 to 90% by weight, the resin (B) is 10 to 40% by weight, and further preferably the polymer fine particles (A) are 60 to 85% by weight and the resin (B) is. It is 15 to 40% by weight, most preferably 60 to 80% by weight of the polymer fine particles (A) and 20 to 40% by weight of the resin (B).

(Other configurations of resin (B))
As used herein, fats and oils and fatty acid esters are also included in the resin (B). Examples of fats and oils that can be suitably used as the resin (B) include epoxidized fats and oils such as epoxidized soybean oil and epoxidized flax oil. As the epoxidized soybean oil, a commercially available product can also be used, and examples thereof include ADEKA Corporation's ADEKA OR O-130P and the like. Examples of the fatty acid ester that can be suitably used as the resin (B) include epoxidized fatty acid esters such as epoxidized fatty acid butyl, epoxidized fatty acid 2-ethylhexyl, epoxidized fatty acid octyl ester, and epoxidized fatty acid alkyl ester.

Epoxidized fats and oils and epoxidized fatty acid esters are sometimes referred to as epoxy-based plasticizers. That is, in the present specification, the epoxy-based plasticizer is also included in the resin (B). Examples of epoxy-based plasticizers other than epoxidized fats and oils and epoxidized fatty acid esters include diepoxystearyl epoxyhexahydrophthalate and di2-ethylhexyl epoxyhexahydrophthalate.

Each of the above-mentioned thermosetting resin, thermoplastic resin, mixture of thermosetting resin and thermoplastic resin, fat and oil, and fatty acid ester can be used by mixing with an antioxidant. In the present specification, the antioxidant is regarded as a part of the resin (B) only when it is used in combination with each of the above-mentioned substances. If only the antioxidant is used, the antioxidant is not considered resin (B).

The antioxidant is not particularly limited. Examples of the antioxidant include (a) a primary antioxidant such as a phenol-based antioxidant, an amine-based antioxidant, a lactone-based antioxidant, a hydroxylamine-based antioxidant, and (b) a sulfur-based antioxidant. Examples thereof include agents, secondary antioxidants such as phosphorus-based antioxidants, and the like. As the antioxidant, a commercially available product can also be used. Examples of commercially available phenolic antioxidants include Irganox 245 manufactured by BASF Japan Ltd.

The resin (B) is a thermosetting resin, a mixture of a thermosetting resin and an antioxidant, a thermoplastic resin, a mixture of a thermoplastic resin and an antioxidant, a fat and oil, a mixture of a fat and an antioxidant, and a fatty acid. It is preferably one or more selected from the group consisting of esters, mixtures of fatty acid esters and antioxidants, epoxy curing agents, and mixtures of epoxy curing agents and antioxidants, preferably epoxy resins, acrylic weights. One or more selected from the group consisting of coalescence, a mixture of an epoxy resin and an antioxidant, a mixture of an acrylic polymer and an antioxidant, and a mixture of an epoxy-based plastic and an antioxidant. More preferably, one or more selected from the group consisting of a mixture of an epoxy resin and an antioxidant, a mixture of an acrylic polymer and an antioxidant, and a mixture of an epoxy-based plastic and an antioxidant. It is even more preferable, and it is particularly preferable that it is a mixture of an epoxy-based plastic agent and an antioxidant. According to this structure, (a) the resin composition containing the obtained granules can provide a cured product or a molded product having excellent heat resistance, and (b) improve the dispersibility of the polymer fine particles (A) in the matrix resin. It has the advantage of being able to.

(2-5. Blocking inhibitor)
As described above, it is preferable to use an anti-blocking agent in the powder or granular material preparation step, and it is preferable that the powder or granular material and the granules contain an anti-blocking agent. According to this structure, the blocking resistance is improved in the production of the polymer fine particles (A), and in the resin composition containing the obtained granules, the polymer fine particles (A) in the matrix resin (C) It has the advantage of better dispersibility. The blocking inhibitor is not particularly limited as long as it has the above-mentioned effects. Examples of the blocking inhibitor include (i) inorganic fine particles such as silicon dioxide, titanium oxide, aluminum oxide, zirconium oxide, aluminum silicate, diatomaceous earth, zeolite, kaolin, talc, calcium carbonate, calcium phosphate, barium sulfate, and magnesium hydrosilicate. Anti-blocking agent; (ii) Anti-blocking agent composed of organic fine particles; (iii) Oil-based anti-blocking agent such as polyethylene wax, higher fatty acid amide, metal calcium, and silicone oil. Among these, as the blocking inhibitor, a blocking inhibitor composed of fine particles (inorganic fine particles or organic fine particles) is preferable, and a blocking inhibitor composed of organic fine particles is more preferable. The blocking inhibitor is a polymer containing a structural unit derived from one or more monomers selected from an aromatic vinyl monomer, a vinyl cyan monomer and a (meth) acrylate monomer as a structural unit. An anti-blocking agent composed of organic fine particles of the above is particularly preferable.

The blocking inhibitor composed of fine particles is generally one in which fine particles are dispersed in a liquid or a colloidal one. The fine particles in the blocking inhibitor have a volume average particle size (Mv) of usually 10 μm or less, preferably 0.05 to 10 μm. The content of the blocking inhibitor is preferably 0.01 to 5.0% by weight, more preferably 0.5 to 3.0% by weight, based on the total weight of the granules.

(2-6. Other optional components)
In this production method, other optional components other than the above-mentioned polymer fine particles (A), resin (B) and blocking inhibitor may be used, if necessary. In other words, the powder or granular material and the granules may contain other optional components other than the polymer fine particles (A), the resin (B) and the blocking inhibitor described above. Examples of other optional components include various components described in the section (4-4. Other optional components) described later.

The anti-blocking agent and other optional components can be appropriately added during any step in the present production method. The anti-blocking agent and other optional components are added to the latex before or after the polymer fine particles (A) or the polymer fine particles (A) and the resin (B) are aggregated, for example, in the powder or granular material preparation step. Can be added. The anti-blocking agent and other optional components can also be added to the polymer fine particles (A) or the powder or granular material containing the polymer fine particles (A) and the resin (B).

(2-6. Granular material)
In the present specification, the “powder / granular material” means an aggregate in which both powder and granules are included, and powders, granules, and the like are collected. Further, when particularly distinguished, "powder" means a particle having a volume average particle diameter of 0.01 mm to 0.1 mm, and "granular material" means a particle having a volume average particle diameter of 0.10 mm to 2.00 mm. do. That is, in the present specification, the “powder / granular material” is intended to be an aggregate of polymer fine particles (A) having a volume average particle diameter of 0.01 mm to 2.00 mm.

The volume average particle size of the powder or granular material is determined by using a laser diffraction type particle size distribution meter (for example, LA-950 manufactured by Horiba Seisakusho) or a dynamic light scattering type particle size distribution meter (for example, Zetasizer ZSP manufactured by Malvern). The dispersion solution of particles can be measured as a sample. Further, the "volume average particle size" of the powder or granular material in the range of less than 10 μm can be measured by using, for example, a dynamic light scattering type (DLS) particle size distribution measuring device Nanotrac WaveII-EX150 (manufactured by Microtrac Bell Co., Ltd.). The "volume average particle size" of the powder or granular material in the range of 10 μm or more can be measured using, for example, a laser diffraction type particle size distribution measuring device Microtrack MT3000II (manufactured by Microtrack Bell Co., Ltd.).

The volume average particle size (Mv) of the powder or granular material is preferably 30 μm to 500 μm, more preferably 30 μm to 300 μm, further preferably 50 μm to 300 μm, and particularly preferably 100 μm to 300 μm. preferable. According to this structure, the powder or granular material has excellent dispersibility of the polymer fine particles (A) in the matrix resin (C). Further, according to the said structure, the powder or granular material provides a highly stable resin composition in which the polymer fine particles (A) are uniformly dispersed in the matrix resin (C) and has a desired viscosity. can. The volume average particle size of the powder or granular material in the range of 10 μm or more is a value obtained by measuring using a laser diffraction type particle size distribution measuring device (Microtrac MT3000II) manufactured by Microtrac Bell Co., Ltd.

Since the obtained powder or granular material has an advantage that it is difficult to contain fine powder having a possibility of dust explosion and coarse particles having poor dispersibility, the number distribution of the volume average particle diameter of the powder or granular material is determined by the volume average particle diameter. It is preferable to have a half price range of 0.5 times or more and 1 times or less of.

The other composition of the powder or granular material is not particularly limited as long as it contains 5.0% by volume or more of powder having a particle diameter of 50 μm or less in 100% by volume of the powder or granular material. The powder or granular material preferably contains 7.5% by volume or more of powder having a particle size of 50 μm or less, more preferably 10.0% by volume or more, in 100% by volume of the powder or granular material. It is more preferable to contain% or more, and it is particularly preferable to contain 20.0% by volume or more. According to this structure, the powder or granular material can be easily formed into granules at 100 ° C. or lower.

The powder or granular material preferably has a D50 particle size of 400 μm or less, more preferably 350 μm or less, more preferably 300 μm or less, further preferably 250 μm or less, and further preferably 200 μm or less. Especially preferable. According to this structure, the powder or granular material can be easily formed into granules at 100 ° C. or lower.

The powder or granular material preferably contains water. The water content (% by weight) in 100% by weight of the powder or granule is preferably 20% by weight to 80% by weight, more preferably 25% by weight to 80% by weight, more preferably 30% by weight to 80% by weight, and 35% by weight. % -80% by weight, more preferably 36% -80% by weight, more preferably 38% -80% by weight, more preferably 40% -80% by weight, 42% -80% by weight. More preferably, 44% by weight to 80% by weight is more preferable, 45% by weight to 80% by weight is more preferable, 50% by weight to 80% by weight is more preferable, 55% by weight to 75% by weight is more preferable, and 60% by weight is 60% by weight. ~ 70% by weight is particularly preferable. According to this structure, the powder or granular material can be easily formed into granules at 100 ° C. or lower.

The powder and granules preferably contain 20% by weight to 80% by weight, more preferably 20% by weight to 75% by weight, and 20% by weight to 70% by weight of the polymer fine particles (A) in 100% by weight of the powders and granules. More preferably, it contains 20% by weight to 65% by weight, more preferably 20% by weight to 64% by weight, more preferably 20% by weight to 62% by weight, and 20% by weight. It is more preferably contained in an amount of about 60% by weight, more preferably 20% by weight to 58% by weight, more preferably 20% by weight to 56% by weight, more preferably 20% by weight to 55% by weight, and 20% by weight. It is more preferably contained in an amount of% to 50% by weight, more preferably 25% by weight to 45% by weight, and particularly preferably 30% by weight to 40% by weight.

(2-7. Granules)
By the above-mentioned production method, agglomerates of granular polymer fine particles (A) can be obtained, that is, granules of polymer fine particles (A) can be obtained. Granules obtained by this production method are also an embodiment of the present invention. The granules according to one embodiment of the present invention (including the granules described in the section [3. Granules] below) are molded products of powder or granular material obtained by molding powder or granular material, that is, polymer fine particles (A). ) Can be said to contain powders and granules formed by agglomeration.

In the present specification, a substance (100% by weight) is placed on a sieve having a mesh size of 1.5 mm, and the sieve is horizontally placed horizontally with a width of 80 mm and once for one round trip, twice per second (one round trip). A substance that remains on the sieve in an amount of 80% by weight or more after sieving (vibrating) for 30 seconds at a high speed is defined as "granule" in the present specification. The sieve to be used is not particularly limited as long as the mesh size is 1.5 mm, but for example, a sieve having an inner diameter of 150 mm and a height of 60 mm can be used.

The granules obtained by this production method preferably have 10 or more voids having ^{an area of 100 μm 2 or more in the fractured surface of the granules.}

[3. Granules]
The granule according to one embodiment of the present invention contains polymer fine particles containing a rubber-containing graft copolymer, and has 10 or more voids having ^{an area of 100 μm 2 or more in a fractured surface.} In the present specification, "granule according to one embodiment of the present invention" may be referred to as "the present granule". Granules can also be called pellets. The terms "granule" and "pellet" are interchangeable.

The granules meet the definition of granules herein above. Therefore, 100% by weight of the present granules are placed on a sieve having an opening of 1.5 mm, and the sieve is horizontally placed horizontally with a width of 80 mm in a width of 80 mm and once in one round trip at a speed of twice per second (one round trip). When sieved (vibrated) for 30 seconds, 80% by weight or more of the granules remain on the sieve. Therefore, the present granules have an advantage that the generation of fine powder is small, and as a result, the granules are hard to scatter and adhere to the body and the device, so that they are easy to handle. Further, the present granules have an advantage that they are easily mixed (difficult to classify) with the granular matrix resin (C).

This granule has 10 or more voids having an area of 100 μm ^{2 or more in a fractured surface.} This is intended that the granules are not granules obtained by melting and molding powder or granular materials at a high temperature. Therefore, the polymer fine particles (A) contained in the present granules have an advantage that the heat load is small, and as a result, a cured product and a molded product in which the granules themselves are less colored and less colored can be provided. The granules preferably have 13 or more voids having an area of 100 μm ² or more, more preferably 15 or more, more preferably 18 or more, and 20 or more in the fractured surface. Is more preferable, 23 or more are more preferable, and 25 or more are particularly preferable. ^{The method for measuring voids having an area of 100 μm 2} or more in the fractured surface of the granules in the present specification will be described in detail in the following Examples.

The granules preferably contain 70% by weight or more of powder or granular material, more preferably 75% by weight or more, more preferably 80% by weight or more, and preferably 85% by weight or more in 100% by weight of the granules. More preferably, it is more preferably 90% by weight or more, and particularly preferably 95% by weight or more.

[4. Resin composition]
[2. Granule production method] Granules obtained by the production method described in the section, or [3. A resin composition containing the granules described in the section [Granules] and the matrix resin (C) is also an embodiment of the present invention. In the present specification, "the resin composition according to one embodiment of the present invention" may be referred to as "the present resin composition".

(4-1. Matrix resin (C))
As the matrix resin (C), a thermosetting resin or a thermoplastic resin can be preferably used.

(4-1-1. Thermosetting resin)
The thermosetting resin is at least one thermosetting selected from the group consisting of a resin containing a polymer obtained by polymerizing an ethylenically unsaturated monomer, an epoxy resin, a phenol resin, a polyol resin, and an amino-formaldehyde resin. It is preferable to contain a sex resin. Further, as the thermosetting resin, a resin containing a polymer obtained by polymerizing an aromatic polyester raw material can also be mentioned. Examples of the aromatic polyester raw material include radically polymerizable monomers such as aromatic vinyl compounds, (meth) acrylic acid derivatives, vinyl cyanide compounds, and maleimide compounds, dimethyl terephthalates, and alkylene glycols. Only one type of these thermosetting resins may be used, or two or more types may be used in combination.

(4-1-2. Thermoplastic resin)
Specific examples of the thermoplastic resin include acrylic polymers, vinyl copolymers, polycarbonates, polyamides, polyesters, polyphenylene ethers, polyurethanes, polyvinyl acetates and the like. Only one type of these may be used, or two or more types may be used in combination.

The acrylic polymer contains an acrylic acid ester monomer as a main component. The acrylic acid ester monomer preferably has 1 to 20 carbon atoms in the ester portion. The acrylic polymer is a homopolymer of an acrylic acid ester monomer, an acrylic acid ester monomer and an unsaturated fatty acid, an acrylamide monomer, a maleimide monomer, a monomer such as vinyl acetate, or the like. Examples thereof include a copolymer with a vinyl-based copolymer. Examples of the acrylic acid ester monomer include methyl acrylate (MA), ethyl acrylate (EA), 2-ethylhexyl acrylate (2EHA), acrylic acid (AA), methacrylic acid (MA), and 2-acrylic acid. Hydroxyethyl (2HEA), 2-hydroxyethyl methacrylate (2HEMA), butyl acrylate (BA), methyl methacrylate (MMA), ethyl methacrylate (EMA) n-butyl methacrylate (nBMA), isobutyl methacrylate (iBMA) ), Chrylic acid (MAA), propyl acrylate, isopropyl acrylate, isobutyl acrylate, t-butyl acrylate, neopentyl acrylate, isodecyl acrylate, lauryl acrylate, tridecyl acrylate, stearyl acrylate, cyclohexyl acrylate, Isobornyl acrylate, tricyclodecynyl acrylate, hydroxyethyl acrylate, hydroxybutyl acrylate, hydroxypropyl acrylate, hydrokissethyl acrylate, 2-methoxyethyl acrylate, dimethylaminoethyl acrylate, chloroethyl acrylate, acrylic Examples thereof include trifluoroethyl acid acid and tetrahydrofurfuryl acrylate. Only one type of these may be used, or two or more types may be used in combination.

In the matrix resin (C), the ratio of the acrylic acid ester monomer to the vinyl-based copolymer, unsaturated fatty acid, acrylamide-based monomer, maleimide-based monomer, and vinyl acetate is as follows. It is preferably 50% by weight to 100% by weight, and the acrylic acid ester monomer is preferably 50% by weight to 100% by weight.

The acrylic polymer preferably contains butyl acrylate (BA) in an amount of 50% by weight or more, more preferably 60% by weight or more, further preferably 70% by weight or more, and particularly preferably 80% by weight or more. It is preferably contained in an amount of 90% by weight or more, most preferably 90% by weight or more.

The vinyl-based copolymer contains one or more monomers selected from the group consisting of aromatic vinyl-based monomers, cyanide-based vinyl monomers, and unsaturated carboxylic acid alkyl ester-based monomers. It is obtained by copolymerizing the mixture. The mixture may further contain other monomers copolymerizable with the monomers described above.

Examples of the aromatic vinyl-based monomer include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene, vinyltoluene and the like. Only one type of these may be used, or two or more types may be used in combination. Among these, styrene is preferable because the refractive index can be easily increased.

The unsaturated carboxylic acid alkyl ester-based monomer is not particularly limited. For example, an ester of an alcohol having 1 to 6 carbon atoms and acrylic acid or methacrylic acid is preferable. The ester of an alcohol having 1 to 6 carbon atoms and acrylic acid or methacrylic acid may further have a substituent such as a hydroxyl group or a halogen group.

Examples of the ester of alcohol having 1 to 6 carbon atoms and acrylic acid or methacrylic acid include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, and (meth) acrylic acid. n-butyl, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, chloromethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) Acrylic acid 2,3,4,5,6-pentahydroxyhexyl, (meth) acrylic acid 2,3,4,5-tetrahydroxypentyl and the like can be mentioned. Only one type of these may be used, or two or more types may be used in combination.

Examples of the vinyl cyanide-based monomer include acrylonitrile, methacrylonitrile, and etacrylonitrile. Only one type of these may be used, or two or more types may be used in combination.

As another monomer copolymerizable with a vinyl-based monomer, an aromatic vinyl-based monomer, a cyanide-based vinyl monomer, and an unsaturated carboxylic acid alkyl ester-based monomer, the effects of the present invention can be obtained. There is no particular limitation as long as it does not impair, and examples thereof include unsaturated fatty acids, acrylamide-based monomers, maleimide-based monomers, vinyl acetate, and acrylic acid ester monomers. Only one type of these may be used, or two or more types may be used in combination.

Examples of unsaturated fatty acids include itaconic acid, maleic acid, fumaric acid, butenoic acid, acrylic acid, and methacrylic acid.

Examples of the acrylamide-based monomer include acrylamide, methacrylamide, N-methylacrylamide and the like.

Examples of maleimide-based monomers include N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-dodecylmaleimide, and N-cyclohexylmaleimide. Examples thereof include N-phenylmaleimide.

The method for producing the vinyl-based copolymer is not particularly limited, and examples thereof include an emulsion polymerization method, a suspension polymerization method, a massive polymerization method, and a solution polymerization method.

In the production of the vinyl-based copolymer, a polymerization initiator may be used if necessary. As the polymerization initiator, for example, one or more kinds are appropriately selected from peroxides, azo compounds, potassium persulfate and the like. obtain.

Examples of the peroxide include benzoyl peroxide, cumene hydroperoxide, dicumyl peroxide, diisopropylbenzene hydroperoxide, t-butyl hydroperoxide, t-butyl peroxyacetate, t-butyl peroxybenzoate, and t. -Butylisopropylcarbonate, di-t-butyl peroxide, t-butylperoctate, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis ( Examples thereof include t-butylperoxy) cyclohexane and t-butylperoxy-2-ethylhexanoate. Of these, cumene hydroperoxide, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, and 1,1-bis (t-butylperoxy) cyclohexane are particularly preferably used. Be done.

Examples of the azo compound include azobisisobutyronitrile, azobis (2,4-dimethylvaleronitrile), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, and 2-cyano-2-propylazo. Formamide, 1,1'-azobiscyclohexane-1-carbonitrile, azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2'-azobisisobutyrate, 1-t-butylazo-2 -Cyanobutane, 2-t-butylazo-2-cyano-4-methoxy-4-methylpentane and the like can be mentioned. Of these, 1,1'-azobiscyclohexane-1-carbonitrile is particularly preferably used.

In the production of the vinyl-based copolymer, the amount of the polymerization initiator added is not particularly limited.

Specific examples of the vinyl-based copolymer include polyvinyl chloride, chlorinated polyvinyl chloride, polystyrene, styrene-acrylonitrile copolymer, styrene-acrylonitrile-N-phenylmaleimide copolymer, and α-methylstyrene-acrylonitrile copolymer weight. Examples thereof include coalescence, polymethyl methacrylate, methyl methacrylate-styrene copolymer, and the like. Only one type of these may be used, or two or more types may be used in combination.

Examples of polyester include polyethylene terephthalate and polybutylene terephthalate.

(4-2. Physical characteristics of matrix resin (C))
The properties of the matrix resin (C) are not particularly limited. The matrix resin (C) is preferably a liquid, a semi-solid, or a solid having a viscosity of 100 mPa · s to 1,000,000 mPa · s at 25 ° C. In addition, "the matrix resin (C) has a viscosity of 100 mPa · s to 1,000,000 mPa · s at 25 ° C." means that "the matrix resin (C) at 25 ° C. has a viscosity of 100 mPa · s ~ 1, It is intended to have a viscosity of ,000,000 mPa · s.

Conventionally, when the matrix resin (C) is a liquid, it has been very difficult to disperse the polymer fine particles (A) in the matrix resin (C) in the form of primary particles. However, in the resin composition according to the embodiment of the present invention, even when the matrix resin (C) is a liquid, the polymer fine particles (A) having the above-mentioned constitution are satisfactorily contained in the matrix resin (C). It has the advantage of being dispersed. Further, when the matrix resin (C) is a liquid, there is an advantage that fusion of the polymer fine particles (A) can be prevented by the matrix resin (C) entering the polymer fine particles (A). When the matrix resin (C) is semi-solid or solid, the obtained resin composition has an advantage that it is less sticky and easy to handle.

The matrix resin (C) preferably has an endothermic peak of 25 ° C. or lower, and more preferably 0 ° C. or lower, according to the differential thermal calorimetry (DSC) thermogram. According to the above configuration, the matrix resin (C) has an advantage of being excellent in fluidity.

When the matrix resin (C) is a thermosetting resin, its state is not particularly limited as long as it flows when mixed with granules, and it may be solid at room temperature, but at room temperature from the viewpoint of workability. Liquid is preferred.

The blending ratio of the granules and the matrix resin (C) is such that the ratio of the contents of the polymer fine particles (A) and the matrix resin (C) in the obtained resin composition is set to a desired value. It can be appropriately set according to a) the content and water content of components other than the polymer fine particles (A) contained in the granules, (b) the method of mixing the granules and the matrix resin (C), and the like.

The ratio of the contents of the polymer fine particles (A) and the matrix resin (C) in the resin composition is usually 100% by weight when the total of the polymer fine particles (A) and the matrix resin (C) is 100% by weight. The polymer fine particles (A) are preferably 0.5 to 50% by weight, the matrix resin (C) is preferably 50 to 99.5% by weight, the polymer fine particles (A) are 1 to 35% by weight, and the matrix resin. It is more preferable that (C) is 65 to 99% by weight, the polymer fine particles (A) are 1.5 to 25% by weight, and the matrix resin (C) is 75 to 98.5% by weight. The polymer fine particles (A) are most preferably 2.5 to 20% by weight, and the matrix resin is most preferably 80 to 97.5% by weight.

(4-3. Organic solvent)
The resin composition preferably contains substantially no organic solvent. When the above-mentioned granules do not substantially contain an organic solvent, a resin composition that does not substantially contain an organic solvent can be obtained. By "substantially free of organic solvent" is intended that the amount of organic solvent in the resin composition is 100 ppm or less.

The amount of the organic solvent (also referred to as the solvent content) contained in the present resin composition is preferably 100 ppm or less, more preferably 50 ppm or less, further preferably 25 ppm or less, and 10 ppm or less. Is particularly preferred. The amount of the organic solvent contained in the present resin composition can be said to be the amount of volatile components (excluding water) contained in the present resin composition. The amount of the organic solvent (volatile component) contained in the present resin composition was reduced by, for example, heating a predetermined amount of the resin composition with a hot air dryer or the like and measuring the weight of the resin composition before and after heating. It can be calculated as the weight. The amount of the organic solvent (volatile component) contained in the present resin composition can also be determined by gas chromatography. Further, when an organic solvent is not used in the production of the present resin composition and the granules contained in the resin composition, the amount of the organic solvent contained in the obtained resin composition can be regarded as 0 ppm.

Examples of the organic solvent substantially not contained in the present resin composition include (a) esters such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate, and (b) acetone, methyl ethyl ketone, diethyl ketone and methyl isobutyl ketone. Ketones, alcohols such as (c) ethanol, (iso) propanol and butanol, ethers such as (d) tetrahydrofuran, tetrahydropyran, dioxane and diethyl ether, and aromatic hydrocarbons such as (e) benzene, toluene and xylene. And (f) halogenated hydrocarbons such as methylene chloride and chloroform.

(4-4. Other optional components)
The present resin composition may contain other optional components other than the above-mentioned components, if necessary. Other optional ingredients include hardeners, colorants such as pigments and dyes, extender pigments, UV absorbers, antioxidants, heat stabilizers (antigels), plasticizers, leveling agents, defoamers, etc. Examples thereof include silane coupling agents, antistatic agents, flame retardant agents, lubricants, thickeners, low shrinkage agents, inorganic fillers, organic fillers, thermoplastic resins, desiccants, and dispersants.

The present resin composition may further contain a known thermosetting resin other than the matrix (C) resin, or may further contain a known thermoplastic resin.

When the present resin composition contains a thermosetting resin as the matrix resin (C), a cured product can be obtained by curing the resin composition. When the present resin composition contains a thermoplastic resin as the matrix resin (C), a molded product can be obtained by molding the resin composition. A cured product obtained by curing the present resin composition and a molded product obtained by molding the present resin composition are also embodiments of the present invention.

Hereinafter, one embodiment of the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. One embodiment of the present invention can be appropriately modified and implemented to the extent that it can be adapted to the above-mentioned or later gist, and all of them are included in the technical scope of the present invention. Unless otherwise specified, in the following Examples and Comparative Examples, "part" means "part by weight" and "%" means "% by weight".

[Evaluation method]
First, the evaluation method of the powder or granular material and the granules produced by Examples and Comparative Examples will be described below.

(Measurement of volume average particle size of elastic body and polymer fine particles (A))
The volume average particle diameter (Mv) of the elastic or polymer fine particles (A) dispersed in the aqueous latex was measured using Nanotrac WaveII-EX150 (manufactured by Microtrac Bell Co., Ltd.). A water-based latex diluted with deionized water was used as a measurement sample. For the measurement, input the refractive index of water and the elastic or polymer fine particles (A) obtained in each production example, and set the sample concentration so that the measurement time is 120 seconds and the loading index is within the range of 1 to 20. I adjusted it.

(Vicat softening temperature measurement method)
The powder or granular material was placed in a hot air convection dryer heated to 50 ° C. to evaporate the water content, and a dry resin was obtained. Using an 8-inch oil-heated roll mill, the obtained dry resin was kneaded at 170 ° C. for 1 minute to form a 1 mm-thick sheet. Five of the obtained sheets were laminated to form a laminated body, and the laminated body was pressure-molded at 180 ° C. for 10 minutes to obtain a molded body having a thickness of 5 mm. Using the obtained molded product, a test was conducted under the conditions of a test start temperature of 40 ° C., a temperature rise rate of 50 ° C./hour, and a test load of 50 N, according to the Vicat softening temperature test method specified in JIS K 7206. As a result, the vicut softening temperature of the rubber-containing graft copolymer contained in the polymer fine particles (A) in the powder or granular material was determined.

(Measuring method of water content in powder or granular material)
The water content of the powder or granular material was measured as follows. Using 5 g of powder or granular material as a sample, the water content was measured by a heat-drying moisture meter (manufactured by A & D, MX-50). The set temperature was 105 ° C. The water content was calculated by the following formula.
Moisture content (%) = (moisture content) / (weight of dried powder and granules + water content) × 100.

(Method for measuring particle size distribution of powders and granules)
The powder or granular material was dispersed in water to prepare a dispersion liquid. The obtained dispersion was subjected to a laser diffraction type particle size distribution measuring device (LA-950 manufactured by HORIBA, Ltd.), and the particle size distribution of the powder or granular material was measured.

From the obtained results, the amount (% by volume) of the powder having a particle size of 50 μm or less contained in 100% by volume of the powder or granular material and the D50 particle size (μm) of the powder or granular material were calculated, and Table 1 respectively. It is shown in "Amount of powder having a particle size of 50 μm or less (% by volume)" and "D50 particle size (μm)".

(Measuring method of bulk specific density of granules)
The bulk specific density of the granules was measured in accordance with JIS K-7365 using a bulk specific gravity measuring device (JIS K-7365 type manufactured by Kuramochi Kagaku Kikai Seisakusho).

(Sieving of granules)
Granules are placed on a sieve with a mesh size of 1.5 mm, an inner diameter of 150 mm, and a height of 60 mm. , Sifted (vibrated) for 30 seconds. Then, the weight of the granules remaining on the sieve is divided by the weight of the granules placed on the sieve (the weight of the granules before sieving), and further multiplied by 100 to obtain the granules remaining on the sieve. The amount (% by weight) was calculated. Based on the obtained results, it was determined based on the following criteria whether or not the sieve had passed through a sieve having an opening of 1.5 mm. The results are shown in the “Passing through the sieve” column of Table 3.
Not passed: 80% by weight or more of granules remain on the sieve Passing: Less than 80% by weight of granules remain on the sieve.

(SEM observation image of granules)
The granules were sufficiently frozen in liquid nitrogen and then split in (a) liquid nitrogen or (b) removed from liquid nitrogen and split within 10 seconds. As a result, in the photograph of the fractured surface of the granules obtained below, the number of ductile fractured surfaces is reduced as much as possible, and the number of brittle fractured surfaces is increased. Next, the fractured surface was photographed with a scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, S-4800) so as to include a square area of at least 500 μm × 500 μm which is the fractured surface of the granule. Specifically, with respect to the fractured surface of the granule, after adjusting the brightness, contrast and focus so that shadows can be observed in the fractured surface, an SEM image with an acceleration voltage of 10.0 kV, a WD of 10 mm and a magnification of 150 times is photographed and acquired. bottom. In addition, SEM images were acquired at least at two locations so that the square areas of 500 μm × 500 μm did not overlap with respect to the fractured surface of one granule.

(Calculation of the area of voids in the fractured surface of granules)
The area of the voids in the fractured surface of the granule was calculated by the following method. All the image processing shown below was performed using the image processing software ImageJ (Version 1.52). For the work (3), image processing software other than ImageJ such as Windows (registered trademark) Paint can also be used.
(1) At least two or more SEM images including a square area of 500 μm × 500 μm, which is a fractured surface, so as not to overlap were captured in ImageJ.
(2) The scale of each SEM image was acquired.
(3) From each SEM image, at least two or more square areas of 500 μm × 500 μm were designated and extracted. The extracted image is hereinafter referred to as an "analyzed image".
(4) In each analysis image, the density of 256 gradations from the minimum value 0 to the maximum value 255 was measured, and each analysis image was binarized to black and white at the threshold value obtained by the following formula.
Threshold = minimum value + (maximum value-minimum value) x 0.15.
(5) In each binarized analysis image, the area and the number of black regions were measured, and the number of black regions having an area of 100 μm ² or more was calculated. For each granule, ^{the total of "the number of black regions having an area of 100 μm 2} or more" is divided by the total number of analysis images (two or more), and the result (that is, the average value) is the area of the granule in the fractured surface of 100 μm. The number of voids was ^{2 or more.} The results are listed in the "Number of voids" column in Table 2.

(Method of preparing test pieces for evaluation of yellowness YI)
Using the obtained granules, a test piece having a thickness of 2 mm was prepared. The procedure for preparing the test piece is described below. The obtained granules and the polycarbonate-based resin were mixed at a ratio of granules: polycarbonate-based resin = 5: 100, and (a) 3- (3,5-di-tert-butyl) was added to the obtained mixture as an antioxidant. Stearyl (-4-hydroxyphenyl) propionate and (b) tris (2,4-di-t-butylphenyl) phosphite were added in an amount of 0.1 part each and mixed to obtain a mixture. Subsequently, the mixture was kneaded with a twin-screw extruder (TEX-44, manufactured by Japan Steel Works, Ltd.), and the kneaded product was extruded to obtain a resin composition. The conditions of the extruder were C2-C9 = 260 ° C. and die temperature = 260 ° C. Subsequently, the obtained resin composition was dried in a dry oven at 120 ° C. for 5 hours. The dried resin composition was molded into ASTM D638-1 type (dumbbell piece) using an injection molding machine (160MSP-10 type, manufactured by Mitsubishi Heavy Industries, Ltd.) to prepare a test piece. The conditions for injection molding were cylinder temperature T3 = 275 ° C., T2 = 280 ° C., T1 = 285 ° C., nozzle temperature N = 285 ° C., and mold temperature = 90 ° C.

(Evaluation method of yellowness YI)
The yellowness YI of the obtained test piece was measured using a color difference meter (model: SE-2000) manufactured by Nippon Denshoku Kogyo Co., Ltd. according to ASTM-E1925. The degree of yellowness YI indicates the degree to which the hue deviates from colorless or white in the yellow direction.

Production Example: Preparation of Latex of Polymer Fine Particles (A) (Production Example 1) <Production of Rubber-Containing Graft Copolymer (B1)>
The following substances were charged into a polymerization apparatus (volume 8 L) equipped with a stirrer.
Deionized water 180 parts Polyoxyethylene lauryl ether phosphoric acid 0.002 parts Boric acid 0.4725 parts Sodium carbonate 0.04725 parts Sodium hydroxide 0.0098 parts.

Next, oxygen was sufficiently removed from the inside of the polymerization apparatus by substituting the gas inside the polymerization apparatus with nitrogen. Then, the temperature in the polymerization apparatus was raised to 80 ° C. Then, 0.027 parts of potassium persulfate was added into the polymerization apparatus with a 2% aqueous potassium persulfate solution. Then, the mixture of the polymerization step (I) shown in Table 1 was continuously added into the polymerization apparatus over 81 minutes. The polymerization (polymerization step (I)) was continued for another 60 minutes to obtain a polymer (I). The polymerization conversion rate was 99.0%.

Then, 0.0267 parts of sodium hydroxide was added into the polymerization apparatus with a 2% aqueous sodium hydroxide solution, and 0.08 parts of potassium persulfate was added into the polymerization apparatus with a 2% aqueous potassium persulfate solution. Then, the mixture of the polymerization step (II) shown in Table 1 was continuously added into the polymerization apparatus over 150 minutes. After completion of the addition, 0.015 parts of potassium persulfate was added with a 2% aqueous potassium persulfate solution. Then, the polymerization (polymerization step (II)) was continued for 120 minutes to obtain a polymer (II). The polymerization conversion rate was 99.0%. The volume average particle size of the obtained polymer (II) was 241 nm.

Then, 0.023 part of potassium persulfate was added with a 2% aqueous potassium persulfate solution. Then, the mixture of the polymerization step (III) shown in Table 1 was continuously added into the polymerization apparatus over 70 minutes. Further, the polymerization (polymerization step (II)) was continued for 60 minutes to obtain a latex containing the rubber-containing graft copolymer (B1), which is the polymer fine particles (A). The polymerization conversion rate was 100.0%.

When the amount of the unreacted alkyl mercaptan chain transfer agent contained in the latex containing the polymer (I) was measured by a gas chromatograph (manufactured by Shimadzu Corporation, GC-2014), the unreacted amount was 0. It was as small as 01% by weight. From the results, it can be estimated that almost all of the added alkyl mercaptan chain transfer agent was converted to the alkylthio group terminal at the time when the polymerization of the polymer (I) was completed.

(Production Example 2) <Production of rubber-containing graft copolymer (B2)>
(Manufacturing Example 2a) <Manufacturing of latex (2a) containing an elastic body>
In a pressure-resistant polymerizer equipped with a stirrer, 200 parts of pure water, 0.03 parts of tripotassium phosphate, 0.0012 parts of ferrous sulfate heptahydrate, 0.008 parts of disodium ethylenediaminetetraacetate (EDTA). And 0.03 part of polyoxyethylene alkyl ether sodium phosphate was added. Next, oxygen was sufficiently removed from the inside of the pressure-resistant polymerizer by replacing the gas inside the pressure-resistant polymerizer with nitrogen while stirring the charged raw materials. Then, 100 parts of butadiene (Bd), 0.05 part of sodium formaldehyde sulfoxylate (SFS) and 0.2 part of paramentan hydroperoxide (PHP) were put into the pressure-resistant polymerizer. Then, 1.4 parts of sodium polyoxyethylene alkyl ether phosphate was added dropwise into the pressure-resistant polymerizer over 6 hours. Then, the reaction solution in the pressure-resistant polymerizer was kept at pH 6.5-7.5 in the reaction solution and the temperature of the reaction solution at 50 ° C. for 10 hours to carry out polymerization. The conversion was 98% by weight. By the polymerization, a latex containing an elastic body (2a) containing polybutadiene rubber as a main component was obtained. The volume average particle size of the elastic body (2a) contained in the obtained latex was 140 nm.

(Production Example 2b) <Production of rubber-containing graft copolymer (B2) (formation of graft portion)>
Latex containing the elastic body (2a) was charged into a glass reactor so as to have a solid content equivalent to about 71 parts. Here, the glass reactor had a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer addition device. The gas in the glass reactor was replaced with nitrogen, and the raw material charged at 60 ° C. was stirred. Next, while keeping the reaction solution in the glass reactor at pH 6.5 to 7.5 in the reaction solution and the temperature of the reaction solution at about 60 ° C., (a) 22 parts of methyl methacrylate (MMA) and styrene (St). 7 parts were continuously added to the glass reactor over 60 minutes, and (b) 0.07 parts of t-butyl hydroperoxide (BHP) and 0.1 part of SFS were added to the glass reactor for 2 hours. The whole amount was added over and polymerized. The addition of MMA and St and the addition of BHP and SFS were started at the same time. After adding all the amounts of BHP and SFS, the reaction solution was further held at about 60 for 1 hour to complete the polymerization. By the polymerization, a latex containing a rubber-containing graft copolymer (B2) which is a polymer fine particle (A) was obtained. The volume average particle size of the polymer fine particles (A) (rubber-containing graft copolymer (B2)) contained in the obtained latex was 200 nm.

(Example 1)
(Powder and granule preparation process)
(Slurry preparation process)
An aqueous calcium chloride solution containing 2.5 parts of calcium chloride with respect to the latex of the rubber-containing graft copolymer (B1) containing 100 parts of the rubber-containing graft copolymer (B1) which is the polymer fine particles (A). (Calcium chloride concentration 25% (w / w)) was added. By such an operation, the polymer fine particles (A) (rubber-containing graft copolymer (B1)) in the latex were aggregated to obtain a slurry containing the agglomerates of the polymer fine particles (A). 200 parts of pure water was added to the obtained slurry. The obtained slurry was heated with stirring (100 times / 1 minute). When the temperature of the slurry reached 45 ° C., the stirring of the slurry was finished.

(Dehydration process and cleaning process)
Then, the obtained slurry is suction-filtered and dehydrated (dehydration step), the obtained aggregates are subjected to washing with water (washing step), and the slurry is suction-filtered again (dehydration step). Got In addition, through all the examples and comparative examples, in the suction filtration of the slurry, No. 2 Using a qualitative filter paper, suction filtration was performed for 3 minutes. The water content of the powder or granular material (R1) was 59.3% by weight.

(Molding process)
The powder or granular material (R1) was supplied to an extrusion compression granulator and molded into granules at 40 ° C. The molding die had a hole diameter of Φ3 mm, a plate thickness of 3 mm, and a hole pitch of 4 mm. The obtained granules were dried by allowing them to stand for one day and night in a dryer at 50 ° C. to obtain granules (P1). The bulk specific gravity of the granules (P1) was 0.35 g / mL. When the voids in the fractured surface of the granule (P1) were measured by the above method, it was confirmed that there were 10 or more voids having ^{an area of 100 μm 2 or more.}

(Example 2)
(Powder and granule preparation process)
(Slurry preparation process)
An aqueous calcium chloride solution (calcium chloride concentration 0.5% (w / w)) was prepared. While stirring the calcium chloride aqueous solution (100 times / minute), a latex containing a rubber-containing graft copolymer (B1) which is a polymer fine particle (A) was added to the calcium chloride aqueous solution to obtain a mixture. .. Here, the mixture was prepared so that the amount of calcium chloride in the mixture was 2.5 parts with respect to 100 parts of the rubber-containing graft copolymer (B1) in the mixture. By such an operation, the polymer fine particles (A) (rubber-containing graft copolymer (B1)) in the latex were aggregated to obtain a slurry containing the agglomerates of the polymer fine particles (A). The obtained slurry was heated with stirring (100 times / 1 minute). When the temperature of the slurry reached 60 ° C., the stirring of the slurry was finished.

(Dehydration process and cleaning process)
Then, the obtained slurry is suction-filtered and dehydrated (dehydration step), the obtained aggregates are subjected to washing with water (washing step), and the slurry is suction-filtered again (dehydration step) to obtain white powders and granules. (R2) was obtained. The water content of the powder or granular material (R2) was 66.4%.

(Molding process)
The powder or granular material (R2) was supplied to an extrusion compression granulator and molded into granules at 50 ° C. The molding die had a hole diameter of Φ3 mm, a plate thickness of 3 mm, and a hole pitch of 4 mm. The obtained resin molded product was dried by allowing it to stand for one day and night in a dryer at 50 ° C. to obtain granules (P2). The bulk specific gravity of the granules (P2) was 0.37 g / mL. When the voids in the fractured surface of the granule (P2) were measured by the above method, it was confirmed that there were 10 or more voids having ^{an area of 100 μm 2 or more.}

(Example 3)
(Powder and granule preparation process)
(Slurry preparation process)
The slurry preparation step was carried out in the same manner as in Example 2.

(Dehydration process and cleaning process)
Then, the obtained slurry is suction-filtered and dehydrated (dehydration step), the obtained aggregates are subjected to washing with water (washing step), and the slurry is suction-filtered again (dehydration step) to obtain white powders and granules. (R3) was obtained. The water content of the powder or granular material (R3) was 64.0%.

(Molding process)
The powder or granular material (R3) was supplied to an extrusion compression granulator and molded into granules at 50 ° C. The molding die had a hole diameter of Φ3 mm, a plate thickness of 3 mm, and a hole pitch of 4 mm. The obtained resin molded product was dried by allowing it to stand for one day and night in a dryer at 50 ° C. to obtain granules (P3). The bulk specific gravity of the granules (P3) was 0.36 g / mL. When the voids in the fractured surface of the granule (P3) were measured by the above method, it was confirmed that there were 10 or more voids having ^{an area of 100 μm 2 or more.}

(Example 4)
(Molding process)
The powder or granular material (R3) was supplied to an extrusion compression granulator and molded into granules at 50 ° C. The molding die had a hole diameter of Φ5 mm, a plate thickness of 5 mm, and a hole pitch of 8 mm. The obtained resin molded product was dried by allowing it to stand for one day and night in a dryer at 50 ° C. to obtain granules (P4). The bulk specific gravity of the granules (P4) was 0.46 g / mL. The voids in fractured granules (P4) was measured by the method described above, the area 100 [mu] m ² or more gaps are present 33, the area 100 [mu] m ² or more 400 [mu] m ² or less of voids was confirmed that there 30.

FIG. 1 shows an SEM image obtained by imaging the fractured surface of the granule (P4) with a scanning electron microscope (SEM) by the above method and a binarized image thereof. FIG. 1 shows an SEM image of the fractured surface obtained by imaging the fractured surface of the granule according to Example 4, that is, one embodiment of the present invention with a scanning electron microscope (SEM), and the SEM image. Is an image after binarization processing. Specifically, the SEM image 1 obtained by imaging the fractured surface of the granules (P4) with a scanning electron microscope (SEM) by the above method is shown on the left side of FIG. 1, and on the right side of FIG. Shows the binarized image 2 obtained by binarizing the SEM image 1 by the above method. As shown in SEM image 1, many voids are observed in the fractured surface of the granule (P4), and it is clear from the binarized image 2 that there are many voids having an ^{area of 100 μm 2 or more in the fractured surface of the granule (P4).} I understand.

(Example 5)
(Powder and granule preparation process)
(Slurry preparation process)
The slurry preparation step was carried out in the same manner as in Example 2.

(Dehydration process and cleaning process)
Then, the obtained slurry is subjected to centrifugal dehydration (dehydration step), the obtained agglomerates are further subjected to water washing (washing step), and the slurry is subjected to centrifugal dehydration again (dehydration step), and white powder or granular material (R5) is subjected to centrifugal dehydration. ) Was obtained. For dehydration, an upper discharge type centrifuge (H-130G) manufactured by Kokusan Co., Ltd. was used. The water content of the powder or granular material (R5) was 44.8%.

(Molding process)
The powder or granular material (R5) was supplied to an extrusion compression granulator and molded into granules at 50 ° C. The molding die had a diameter of 5 mm, a plate thickness of 5 mm, and a hole pitch of 8 mm. The obtained resin molded product was dried by allowing it to stand for one day and night in a dryer at 50 ° C. to obtain granules (P5). The bulk specific gravity of the granules (P5) was 0.29 g / mL. When the voids in the fractured surface of the granule (P5) were measured by the above method, it was confirmed that there were 10 or more voids having ^{an area of 100 μm 2 or more.}

(Example 6)
(Powder and granule preparation process)
An aqueous calcium chloride solution (calcium chloride concentration 1.0% (w / w)) was prepared. Further, IRGANOX-1076 [n-], which is a phenolic antioxidant, is added to the latex of the rubber-containing graft copolymer (B2) containing 100 parts of the rubber-containing graft copolymer (B2) which is the polymer fine particles (A). Octadecyl-3- (3', 5', di-t-butyl-4'-hydroxyphenyl) propionate] 2 parts was added to prepare a latex containing an antioxidant. A latex containing an antioxidant was added to the calcium chloride aqueous solution while stirring the calcium chloride aqueous solution (100 times / minute) to obtain a mixture. Here, the mixture was prepared so that the amount of calcium chloride in the mixture was 4.0 parts with respect to 100 parts of the rubber-containing graft copolymer (B2) in the mixture. By this operation, the polymer fine particles (A) (rubber-containing graft copolymer (B2)) in the latex were agglutinated to obtain a slurry containing the agglomerates of the polymer fine particles (A). The obtained slurry was heated with stirring (100 times / 1 minute). When the temperature of the slurry reached 70 ° C., the stirring of the slurry was finished.

(Dehydration process and cleaning process)
Then, the obtained slurry is suction-filtered and dehydrated (dehydration step), the obtained aggregates are subjected to washing with water (washing step), and the slurry is suction-filtered again (dehydration step) to obtain white powders and granules. (R6) was obtained. The water content of the powder or granular material (R6) was 61.2%.

(Molding process)
The powder or granular material (R6) was supplied to an extrusion compression granulator and molded into granules at 50 ° C. The molding die had a hole diameter of Φ5 mm, a plate thickness of 5 mm, and a hole pitch of 8 mm. The obtained resin molded product was dried by allowing it to stand for one day and night in a dryer at 50 ° C. to obtain granules (P6). The bulk specific gravity of the granules (P6) was 0.33 g / mL. The voids in fractured granules (P6) was measured by the method described above, the area 100 [mu] m ² or more gaps are present 50, the area 100 [mu] m ² or more 400 [mu] m ² or less of voids was confirmed that there 36.

(Example 7)
(Powder and granule preparation process)
(Slurry preparation process)
IRGANOX-1076 [n-octadecyl-], which is a phenolic antioxidant, is added to the latex of the rubber-containing graft copolymer (B2) containing 100 parts of the rubber-containing graft copolymer (B2) which is the polymer fine particles (A). 3- (3', 5', di-t-butyl-4'-hydroxyphenyl) propionate] was added to prepare a latex containing an antioxidant. The obtained latex is subjected to an average droplet of the latex in a device having a cylindrical shape with a height of 6 m and a diameter of 60 cm and an atmospheric pressure atmosphere using a swirling flow type empty conical nozzle which is a kind of pressure nozzle. The droplets were sprayed at a spray pressure of 2 MPa so as to be dispersed as droplets having a diameter of about 150 μm. At the same time, an aqueous solution of calcium chloride (calcium chloride concentration 50% (w / w)) in an amount such that 4.2 parts of calcium chloride is obtained with respect to 100 parts of the graft-containing copolymer (B2) in the sprayed latex. The calcium chloride aqueous solution was sprayed into the apparatus so as to form a smoke atom. When Luotech and the calcium chloride aqueous solution come into contact with each other while falling in the cylinder, the polymer fine particles (A) (rubber-containing graft copolymer (B2)) in the latex are aggregated, and the aggregate is heated to 60 ° C. It was collected by a receiving tank at the bottom of the device filled with water. By such an operation, a slurry containing an aggregate of the polymer fine particles (A) was obtained.

(Dehydration process and cleaning process)
Then, the obtained slurry is suction-filtered and dehydrated (dehydration step), the obtained agglomerates are subjected to washing with water (washing step), and the slurry is suction-filtered again (dehydration step) to obtain white powders and granules. (R7) was obtained. The water content of the powder or granular material (R7) was 65.2%.

(Molding process)
The powder or granular material (R7) was supplied to an extrusion compression granulator and molded into granules at 50 ° C. The molding die had a hole diameter of Φ5 mm, a plate thickness of 5 mm, and a hole pitch of 8 mm. The obtained resin molded product was dried by allowing it to stand for one day and night in a dryer at 50 ° C. to obtain granules (P7). The bulk specific gravity of the granules (P7) was 0.22 g / mL. When the voids in the fractured surface of the granule (P7) were measured by the above method, it was confirmed that there were 10 or more voids having ^{an area of 100 μm 2 or more.}

(Comparative Example 1)
(Powder and granule preparation process)
(Slurry preparation process)
An aqueous calcium chloride solution containing 2.5 parts of calcium chloride with respect to the latex of the rubber-containing graft copolymer (B1) containing 100 parts of the rubber-containing graft copolymer (B1) which is the polymer fine particles (A). (Calcium chloride concentration 25% (w / w)) was added. By such an operation, the polymer fine particles (A) (rubber-containing graft copolymer (B1)) in the latex were aggregated to obtain a slurry containing the agglomerates of the polymer fine particles (A). 200 parts of pure water was added to the obtained slurry. The obtained slurry was heated with stirring (100 times / 1 minute). When the temperature of the slurry reached 90 ° C., the stirring of the slurry was finished.

(Dehydration process and cleaning process)
Then, the obtained slurry is suction-filtered and dehydrated (dehydration step), the obtained aggregates are subjected to washing with water (washing step), and the slurry is suction-filtered again (dehydration step) to obtain white powders and granules. (RR1) was obtained. The water content of the powder or granular material (RR1) was 37.5%.

(Molding process)
The powder or granular material (RR1) was supplied to an extrusion compression granulator, and an attempt was made to form it into granules at 50 ° C. The molding die had a hole diameter of Φ3 mm, a plate thickness of 3 mm, and a hole pitch of 4 mm. The powder or granular material (RR1) was not molded, and the powder or granular material (RR1) was discharged as it was.

(Comparative Example 2)
(Powder and granule preparation process)
Water was added to and mixed with the powder or granular material (RR1) obtained in Comparative Example 1 to obtain a humidity-controlled powder or granular material (RR2). The water content of the powder or granular material (RR2) was 65.0%.

(Molding process)
The powder or granular material (RR2) was supplied to an extrusion compression granulator, and an attempt was made to form it into granules at 50 ° C. The molding die had a hole diameter of Φ3 mm, a plate thickness of 3 mm, and a hole pitch of 4 mm. The powder or granular material (RR2) was not molded, and the powder or granular material (RR2) was discharged as it was.

(Comparative Example 3)
The powder or granular material (R7) was extruded and kneaded using a twin-screw extruder to form granules to obtain granules (PR3). The molding conditions of the extruder were a barrel temperature of 150 ° C. and a die discharge hole diameter of Φ4 mm. The bulk specific gravity of the granules obtained by cutting the extruded strand, which is a melt-kneaded product having a diameter of 4 mm, in water was 0.43 g / mL. When the voids in the fractured surface of the granule (PR3) were measured by the above method, it was confirmed that ^{there were three voids having an area of 100 μm 2} or more and two voids having an area of 100 μm ² or more and 400 μm ^{2 or less.}

FIG. 2 shows an SEM image obtained by imaging the fractured surface of the granule (PR3) with a scanning electron microscope (SEM) by the above method and a binarized image thereof. FIG. 2 shows an SEM image of the fractured surface obtained by imaging the fractured surface of the granule of Comparative Example 3 with a scanning electron microscope (SEM), and an image obtained by binarizing the SEM image. be. Specifically, the SEM image 3 obtained by imaging the fractured surface of the granule (PR3) with a scanning electron microscope (SEM) by the above method is shown on the left side of FIG. 2, and is shown on the right side of FIG. Shows the binarized image 4 obtained by binarizing the SEM image 3 by the above method. As shown in SEM image 1, no voids are observed in the fractured surface of the granule (PR3), and from the binarized image 2, there are only a few voids having an ^{area of 100 μm 2 or more in the fractured surface of the granule (PR3).} I can clearly see it.

(Reference example)
The powder or granular material R6 was mixed with a polycarbonate resin to prepare a test piece for evaluating the yellowness YI by the above method. The yellowness YI of the test piece was -39.5.

(Example 8)
Granules P6 were mixed with a polycarbonate resin to prepare a test piece for evaluation of yellowness YI by the above method. The yellowness YI of the test piece was -38.8.

(Comparative Example 4)
The granules (PR3) were mixed with a polycarbonate resin to prepare a test piece for evaluation of yellowness YI by the above method. The yellowness of the test piece was -27.6.

It is known that a resin subjected to a heat load has an increased yellowness due to oxidative deterioration. As shown in Table 4, it can be seen that the granules of the present invention exhibit better color tone characteristics as compared with pellets that have undergone melt extrusion because the heat load is suppressed.

According to one embodiment of the present invention, granules containing the polymer fine particles can be easily provided without melting the polymer fine particles at a high temperature. The granules obtained by one embodiment of the present invention are, for example, (a) applications for electrical and electronic parts such as personal computers, liquid crystal displays, projectors, smartphones, etc .; , Building materials such as doors; (c) Vehicle applications such as handles, shift levers, vibration isolators, driver's seat panels; (d) Adhesives, coating materials, reinforcing fiber binders, composite materials, 3D printer modeling materials, It can be suitably used for applications such as a sealant and an electronic substrate.

Claims (5)

Including a molding step of molding a powder or granular material at a temperature of 100 ° C. or lower,
The powder or granular material contains polymer fine particles containing a rubber-containing graft copolymer, and contains
The method for producing granules, wherein the powder or granular material contains 5.0% by volume or more of powder having a particle diameter of 50 μm or less in 100% by volume of the powder or granular material. The method for producing granules according to claim 1, wherein the powder or granular material has a D50 particle size of 400 μm or less. The method for producing granules according to claim 1 or 2, wherein 10 or more voids having an area of 100 μm ^{2 or more are present in the fractured surface of the granules.} Prior to the molding step, a powder / granular material preparation step of obtaining a powder / granular material of the polymer fine particles from the latex containing the polymer fine particles is further included.
The method for producing granules according to any one of claims 1 to 3, wherein in the powder / granule preparation step, the polymer fine particles are handled at a temperature equal to or lower than the Vicat softening temperature of the rubber-containing graft copolymer. Contains polymer microparticles, including rubber-containing graft copolymers,
Granules having 10 or more voids having an area of 100 μm ^{2 or more in a fractured surface.}

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