Method for manufacturing powder and granule, and powder and granule

Abstract

An object of the present invention is to provide a method for recovering polymer particles from a latex containing polymer particles without using an electrolyte and an organic solvent. The method for producing the powder of the present invention includes an impregnation step of impregnating a gas into a latex containing polymer particles and a spraying step of spraying the latex after the heating step and the impregnation step, and the polymer particles include a graft copolymer having a graft portion.

Description

Technical Field

[0001] The present invention relates to a method for producing a powder or granule and a powder or granule. Background Art

[0002] 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 has been widely used.

[0003] In most cases, polymer fine particles are obtained in the form of a latex, and thus it is necessary to recover the polymer fine particles from the latex. As methods for recovering polymer fine particles from a latex containing polymer fine particles, there are known: (a) a method of adding an electrolyte to the latex to inactivate an emulsifier to obtain an aggregate of polymer fine particles, and (b) a method of adding an organic solvent and water to the latex and utilizing the difference in solubility of the organic solvent and water to obtain an aggregate of polymer fine particles.

[0004] In addition, as a method for drying an aggregate of polymer fine particles, there is known a method of spraying a latex to form droplets and then drying the droplets to obtain an aggregate of polymer fine particles as disclosed in Patent Documents 1 to 6.

[0005] Prior Art Documents

[0006] Patent Documents

[0007] Patent Document 1: Japanese Published Patent Gazette "Japanese Unexamined Patent Application Publication No. 2002-308997"

[0008] Patent Document 2: Japanese Published Patent Gazette "Japanese Unexamined Patent Application Publication No. 2016-164283"

[0009] Patent Document 3: International Published Gazette "WO2013-129709"

[0010] Patent Document 4: Japanese Published Patent Gazette "Japanese Unexamined Patent Application Publication No. 2008-297339"

[0011] Patent Document 5: Japanese Published Patent Gazette "Japanese Unexamined Patent Application Publication No. 2003-155350"

[0012] Patent Document 6: Japanese Published Patent Gazette "Japanese Unexamined Patent Application Publication No. 2001-329067" Summary of the Invention

[0013] Problems to be Solved by the Invention

[0014] As a method for recovering polymer fine particles from a latex containing polymer fine particles, new technology is required.

[0015] The present invention has been accomplished in view of the above problems, and an object thereof is to provide a method for recovering polymer particles from a latex containing polymer particles without using an electrolyte and an organic solvent.

[0016] Method for Solving the Problems

[0017] The inventors of the present invention conducted intensive studies to solve the above problems, and as a result, found that by impregnating a gas into a latex containing polymer particles and then spraying the latex, it is possible to efficiently recover polymer particles from the latex containing polymer particles without using an electrolyte and an organic solvent, thereby completing the present invention.

[0018] That is, a method for manufacturing a powder according to one embodiment of the present invention includes an impregnation step of impregnating a gas into a latex containing polymer particles, and a spraying step of spraying the latex, wherein the polymer particles include a graft copolymer having a graft portion.

[0019] In addition, a powder according to one embodiment of the present invention is a powder obtained by aggregating polymer particles, the polymer particles (a) include a graft copolymer having a graft portion, and (b) have a volume average particle diameter of 0.03 μm to 2.00 μm, and the disintegration rate of the powder is 5% or less. Here, the disintegration rate means a value obtained by dividing the weight of the powder passing through a sieve with a mesh size of 4 mm by the weight of the molded product before sieving after compacting the powder with a cylindrical roller having a diameter of 17 mm at a pressure of 100 kPa or more to produce a molded product, and multiplying the obtained value by 100.

[0020] In addition, a particle according to one embodiment of the present invention is a particle including a powder obtained by aggregating polymer particles, the polymer particles (a) include a graft copolymer having a graft portion, and (b) have a volume average particle diameter of 0.03 μm to 2.00 μm, and the disintegration rate of the particle is 5% or less. Here, the disintegration rate means a value obtained by dividing the weight of the powder passing through a sieve with a mesh size of 4 mm by the weight of the particle before sieving when the particle is passed through the sieve, and multiplying the obtained value by 100.

[0021] Effects of the Invention

[0022] According to one embodiment of the present invention, it is possible to recover polymer particles from a latex containing polymer particles without using an electrolyte and an organic solvent. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1It is a graph showing the volume-average particle size distribution of polymer particles (A) dispersed in a latex containing polymer particles, a dispersion aqueous solution of powder B obtained in Example 2, or a dispersion aqueous solution of powder C obtained in Comparative Example 2. Detailed Description

[0024] Hereinafter, an embodiment of the present invention will be described, but the present invention is not limited thereto. The present invention is not limited to each configuration described below, and various modifications can be made within the scope shown in the claims. In addition, embodiments or examples obtained by appropriately combining technical means separately disclosed in different embodiments or examples are also included in the technical scope of the present invention. Furthermore, new technical features can be formed by combining the technical means separately disclosed in each embodiment. It should be noted that all academic documents and patent documents described in this specification are incorporated herein by reference. In addition, in this specification, unless otherwise specified, "A to B" representing a numerical range means "A or more (including A and greater than A) and B or less (including B and less than B)".

[0025] 〔1. Technical Idea of an Embodiment of the Present Invention〕

[0026] The inventors of the present invention conducted in-depth research to provide a new technique for recovering polymer particles from a latex containing polymer particles without using electrolytes and organic solvents. In the process, the inventors independently found the following insight: in a latex containing polymer particles, as long as the affinity between the polymer particles and the solvent in the latex can be reduced, the polymer particles can be recovered in the form of aggregates. Based on this insight, the inventors of the present invention conducted in-depth research on a method for reducing the affinity between polymer particles and the solvent of the latex without using electrolytes and organic solvents. As a result, the inventors independently found the following insight: by impregnating a gas into a latex containing polymer particles and then spraying the latex, the affinity between the polymer particles and the solvent of the latex can be effectively reduced, thereby completing the present invention.

[0027] The reason why the affinity between polymer particles and the solvent of the latex can be effectively reduced by impregnating a gas into a latex containing polymer particles and then spraying the latex is speculated as follows. It can be speculated that when a gas is impregnated into the latex and the latex is sprayed, the impregnated gas expands rapidly, and the gas is released from the sprayed latex (hereinafter, also referred to as latex droplets). As the gas is released from the latex droplets, a shear force is applied to the latex droplets, and as a result, the polymer particles in the latex droplets aggregate. It should be noted that an embodiment of the present invention is not limited to this speculation.

[0028] 〔2. Method for Manufacturing Powders〕

[0029] A method for producing a powder or granule according to an embodiment of the present invention includes an impregnation step of impregnating a gas into a latex containing polymer particles, and a spraying step of spraying the latex after the impregnation step. Here, the polymer particles contain a graft copolymer having a graft portion. Sometimes, the method for producing a powder or granule according to an embodiment of the present invention is also referred to as this production method. The powder or granule obtained by this production method becomes a resin composition after being dispersed in a matrix resin described later.

[0030] According to this production method, since no electrolyte such as a coagulant is used, a powder or granule with low inclusions (low impurities) can be obtained. Inclusions in the powder or granule can have an adverse effect on the physical properties of the cured product or molded article of the resin composition containing the obtained powder or granule. Therefore, the resin composition containing the powder or granule obtained by this production method can provide a cured product or molded article with good physical properties. Specifically, since the powder or granule obtained by this production method has few ions (such as metal ions and chloride ions) derived from the electrolyte, when forming a resin composition, for example, denaturation and decomposition of the matrix resin in a high-temperature environment can be suppressed. Thus, the resin composition, and the cured product or molded article of the resin composition have good quality. The quality of the matrix resin is evaluated by measuring changes in the strength and hue of the cured product or molded article of the resin composition.

[0031] In this production method, since no electrolyte is used, an operation of washing off the electrolyte is not required. Therefore, in this production method, no special washing process is needed, and a large amount of washing water does not need to be used as in the prior art. Thus, the production cost of this production method is excellent. This production method does not use organic solvents, so it has the advantage of a small environmental burden.

[0032] In this production method, compared with the prior art, a powder or granule with a higher moisture content can be obtained. Therefore, in this production method, compared with the prior art, when forming a resin composition, a powder or granule with more excellent dispersibility of polymer particles (A), less generation of fine powder, and easy formation of granules as described later can be provided. By making the dispersibility of polymer particles (A) more excellent when forming a resin composition, the resin composition containing the powder or granule obtained by this production method can provide a cured product or molded article with good physical properties. The fine powder generation of the powder or granule obtained by this production method is less, so it is excellent in terms of operational hygiene. The powder or granule obtained by this production method can easily form granules, so the operability is excellent. "Can easily form granules" is also referred to as "excellent moldability".

[0033] In this specification, "powder particles" includes both powders and granules, and refers to an aggregate formed by the aggregation of powders, granules, etc. In particular, when making a distinction, "powder" refers to a volume average particle size of 0.01 mm to 0.1 mm, and "granule" refers to a volume average particle size of 0.1 mm to 10 mm. The volume average particle size of the powder particles can be measured using a laser diffraction particle size distribution analyzer (for example, LA-950 manufactured by Horiba, Ltd.) or a dynamic light scattering particle size distribution analyzer (for example, Zetasizer ZSP manufactured by Malvern) with a dispersion solution of the powder particles as a sample. In addition, the measurement can also be performed as follows. The "volume average particle size" in the range less than 10 μm can be measured using a dynamic light scattering (DLS) particle size distribution measuring device Nanotrac WaveII-EX150 (manufactured by MicrotracBEL), and the "volume average particle size" in the range of 10 μm or more can be measured using a laser diffraction particle size distribution measuring device Microtrac MT3000II (manufactured by MicrotracBEL).

[0034] In this specification, "polymer fine particles" are sometimes referred to as "polymer fine particles (A)", and "matrix resin" is sometimes referred to as "matrix resin (C)".

[0035] The powder particles obtained by this production method can be said to be an aggregate containing polymer fine particles (A), and can also be said to be agglomerated particles of polymer fine particles (A). This production method can be said to be a method for obtaining an aggregate containing polymer fine particles (A).

[0036] As described above, polymer fine particles (A) can be recovered from a latex containing polymer fine particles (A) by reducing the affinity between polymer fine particles (A) and the solvent in the latex. Therefore, in this production method, a method of further reducing the affinity between polymer fine particles (A) and the solvent in the latex is preferably used. In this specification, the "affinity between polymer fine particles (A) and the solvent in the latex" is sometimes abbreviated as "affinity".

[0037] Hereinafter, after explaining each step of this production method in detail, polymer fine particles (A), etc. will be explained.

[0038] (2-1. Impregnation step)

[0039] The impregnation step is a step of impregnating a gas into a latex containing polymer fine particles (A). The impregnation step can be said to be a step of obtaining a latex containing polymer fine particles (A) and impregnated with a gas.

[0040] In the impregnation step, as a method for impregnating a gas into a latex containing polymer particles (A) (hereinafter, also referred to as a gas impregnation method), there is no particular limitation, and a known method can be used. As the gas impregnation method, for example, a method of applying pressure to the latex and the gas in a state where the latex is in contact with the gas, a method of feeding gas into the latex, and a method of cooling the latex and the gas in a state where the latex is in contact with the gas can be preferably exemplified.

[0041] The above-mentioned gas is not particularly limited, and nitrogen, oxygen, air, hydrogen, carbon dioxide, argon, helium, etc. can be preferably exemplified.

[0042] In this manufacturing method, the above-mentioned gas preferably contains one or more selected from nitrogen, oxygen, and air. Based on this configuration, there are advantages of reducing production costs and enabling safe production.

[0043] (2-2. Pressurization step)

[0044] The above-mentioned impregnation step preferably further has a pressurization step of applying a pressure of 0.5 MPa or more to the above-mentioned latex. The pressurization step can specifically be a step of applying a pressure of 0.5 MPa or more to the latex and the gas in a state where the latex is in contact with the gas, or a step of applying a pressure of 0.5 MPa or more to the latex using the gas in a state where the latex is in contact with the gas. With this configuration, the amount of gas impregnated in the latex can be increased, so the affinity can be further reduced, and thus an aggregate containing polymer particles (A), that is, a powder particle, can be easily obtained.

[0045] In the pressurization step, as a method for applying pressure to the latex, there is no particular limitation, and a known method can be used. As a method for applying pressure to the latex, for example, a method of accommodating the latex in a sealable container, filling it with gas, and after sealing the container, raising the pressure inside the container (hereinafter, also referred to as Method A); and a method of pressurizing by the ejection pressure of a pump can be preferably exemplified. In the case of implementing Method A, the pressure applied to the latex can be measured by a pressure gauge provided on the sealable container.

[0046] In the pressurization step, the pressure applied to the latex is preferably 0.5 MPa or more, more preferably 1.0 MPa or more, further preferably 1.5 MPa or more, still further preferably 2.0 MPa or more, and particularly preferably 2.5 MPa or more.

[0047] In the pressurization step, the time for applying pressure to the latex is not particularly limited. The time for applying pressure to the latex is, for example, preferably 0 minutes to 20 minutes, more preferably 0 minutes to 10 minutes, further preferably 0 minutes to 5 minutes. The time for applying pressure to the latex can be 0 minutes to 1 minute.

[0048] (2-3. Spraying process)

[0049] The spraying process is a process that includes the latex after the impregnation process, i.e., polymer particles (A), and sprays the latex impregnated with gas. The spraying process can be said to be a process of dropletizing the latex after the impregnation process, or a process of preparing latex droplets. Aggregates containing polymer particles (A), i.e., powder particles, can be obtained through the spraying process.

[0050] In the spraying process, as the method for spraying the latex, there is no particular limitation, and known methods can be used. As the method for spraying the latex, for example, a method using a spraying device can be cited. The spraying device is sometimes also called a dropletizing device and a particle atomizing device for liquids. As the spraying device, there is no particular limitation, and examples include: two-fluid injection valves (e.g., atomizers) and pressure injection valves (e.g., single-hole nozzles), etc. The spraying device is preferably a device capable of spraying pressurized liquid.

[0051] The aperture diameter (diameter) of the spray holes of the spraying device used in the spraying process is not particularly limited. The aperture diameter of the spray holes is preferably 1 mm to 10 mm, more preferably 1 mm to 8 mm, and particularly preferably 1 mm to 5 mm.

[0052] The diameter of the droplets of the latex after spraying in the spraying process is not particularly limited. The diameter of the latex droplets is preferably 50 μm to 5 mm, more preferably 100 μm to 800 μm, and further preferably 150 μm to 600 μm.

[0053] The spraying process preferably further has a process of applying pressure to the latex. After applying pressure to the latex, by spraying the latex, the momentum of the latex during spraying can be increased. As a result, the affinity can be further reduced, and thus aggregates containing polymer particles (A), i.e., powder particles, can be easily obtained. In addition, the amount of unaggregated polymer particles (A) in the latex droplets can be reduced.

[0054] As the method for applying pressure to the latex in the spraying process, there is no particular limitation, and known methods can be used. As the method for applying pressure to the latex, for example, the following can be preferably exemplified: (a) a method of accommodating the latex in a sealable container, sealing the container, and then increasing the pressure inside the container; (b) a method of filling the latex in a sealable container with a variable internal volume and reducing the internal volume of the container, and a method of pressurizing by the ejection pressure of a pump, etc. As the sealable container with a variable internal volume, for example, a container equipped with a piston and a syringe can be cited.

[0055] In the spraying step, the method of applying pressure to the latex includes a preferred method, which can be the same as the method of applying pressure to the latex in the pressurizing step in the above-mentioned impregnation step.

[0056] The pressure applied to the latex in the above-mentioned pressurizing step by Method A can be used to spray the latex. For example, (i) the latex is contained in a sealable container, filled with gas, and after sealing the container, the pressure inside the container is increased; (ii) then, the latex inside the container is released from an arbitrary ejection hole to a pressure region with a lower pressure inside the container, whereby the latex can be sprayed. It can be said that the above-mentioned pressurizing step can also serve as the step of applying pressure to the latex in the spraying step. When the latex is sprayed by the method having (i) and (ii) above, the pressure applied to the latex can be measured by a pressure gauge provided in the sealed container.

[0057] (2-4. Heating step)

[0058] This manufacturing method preferably further includes a heating step of heating the latex before the spraying step. With this configuration, the affinity can be further reduced, and thus it is possible to easily obtain an aggregate containing the polymer particles (A), that is, a powder particle.

[0059] The reason why the affinity can be further reduced by the heating step is speculated as follows. By heating the latex, the adhesion between the polymer particles (A) in the latex increases. In addition, when the latex is a latex containing polymer particles (A) obtained by emulsion polymerization, by heating the latex, the emulsifier in the latex is destroyed by hydrolysis, and the emulsifying ability of the emulsifier can be reduced. By the increase in adhesion and sometimes the reduction in emulsifying ability, the dispersion stability of the polymer particles (A) in the latex is reduced, and in the spraying step, the latex with reduced dispersion stability of the polymer particles (A) is sprayed. It can be speculated that as a result, the sprayed latex is likely to be atomized, the affinity between the polymer particles (A) and the solvent in the latex is reduced, and the aggregation of the polymer particles (A) is likely to occur. One embodiment of the present invention is not limited to this speculation.

[0060] The heating step may be carried out before the spraying step, and can be carried out at any stage before and after the impregnation step, or can be carried out simultaneously with the impregnation step (during the impregnation step). In addition, when the heating step and the impregnation step are carried out simultaneously, the pressurizing step and the heating step in the impregnation step can be carried out simultaneously. When the pressurizing step and the heating step are carried out simultaneously, there is an advantage that the heating temperature in the heating step can be increased (described below).

[0061] In the heating step, the temperature at which the latex is heated (also referred to as the heating temperature) is not particularly limited. The heating temperature in the heating step is preferably equal to or higher than the glass transition temperature of the grafted portion of the polymer particles (A). With this configuration, the adhesion between the polymer particles (A) in the latex is further improved, and thus the affinity can be further reduced. As a result, it is possible to more easily obtain aggregates containing the polymer particles (A), that is, powder particles.

[0062] Specifically, the heating temperature is preferably 50°C or higher, more preferably 70°C or higher, still more preferably 100°C or higher, and particularly preferably 120°C or higher.

[0063] In the heating step, the time for heating the latex (also referred to as the heating time) is not particularly limited. This heating time is preferably 1 minute to 60 minutes, more preferably 1 minute to 45 minutes, still more preferably 1 minute to 30 minutes, and particularly preferably 1 minute to 15 minutes.

[0064] (2-5. Stirring step)

[0065] This production method may further include a step of stirring the latex between the above-mentioned impregnation steps and / or between the above-mentioned heating steps. When this production method further has a stirring step, the impregnation efficiency of the gas in the latex in the impregnation step and / or the heating efficiency in the heating step can be further improved. In addition, when this production method further has a stirring step, there is also an advantage that the latex supplied to the spraying step can be made more uniform.

[0066] In the stirring step, the method of stirring the latex is not particularly limited. As a method of stirring the latex, for example, a method of performing the impregnation step and / or the heating step in a container equipped with a stirrer having a stirring blade and stirring the latex with this stirrer can be preferably exemplified.

[0067] In the stirring step, the stirring speed is not particularly limited. In addition, in the stirring step, the time for stirring the latex (also referred to as the stirring time) is not particularly limited.

[0068] (2-6. Resin mixing step)

[0069] This production method may further include a resin mixing step of mixing a resin in the latex containing the polymer particles (A) before the spraying step. Hereinafter, the resin mixed with the latex in the resin mixing step is sometimes also referred to as "resin (B)". The resin mixing step can be said to be a step of adding and mixing the resin (B) in the latex containing the polymer particles (A).

[0070] When the manufacturing method includes a resin mixing step, the obtained powder particles may contain polymer particles (A) and a resin (B). When the obtained powder particles contain polymer particles (A) and a resin (B), the powder particles can be said to be an aggregate containing polymer particles (A) and a resin (B), or can be said to be agglomerated particles of polymer particles (A) and a resin (B).

[0071] The resin mixing step may be carried out before the spraying step, and can be carried out at any stage before and after the impregnation step and before and after the heating step, or can be carried out simultaneously with the impregnation step and / or the heating step (at a stage during the impregnation step and / or the heating step).

[0072] The method of adding the resin (B) to the polymer particles (A) can use various methods and is not particularly limited. For example, there can be mentioned: a method of directly adding the resin (B) to the latex of the polymer particles (A), a method of adding to the latex of the polymer particles (A) in a state where the resin (B) is previously emulsified with water (aqueous emulsion state), or a method of adding to the latex of the polymer particles (A) in a solution state where the resin (B) is dissolved, etc. Among them, a method of adding to the latex of the polymer particles (A) in a state where the resin (B) is previously emulsified with water (aqueous emulsion state) is preferred.

[0073] In addition, the method of mixing the polymer particles (A) and the resin (B) is also not particularly limited. For example, there can be mentioned: for the latex containing the polymer particles (A) and the resin (B), (a) a method of stirring and (b) a method of kneading with a continuous kneader, etc.

[0074] (2 - 7. Cleaning step)

[0075] The manufacturing method may further include a cleaning step of cleaning the powder particles obtained in the spraying step. By cleaning the powder particles, powder particles with a lower content of inclusions and the like can be obtained. The cleaning step is more preferably carried out with water, and even more preferably carried out with ion-exchanged water or pure water.

[0076] The cleaning step is only required to be a step of cleaning the powder particles, and there is no particular limitation on the specific method. For example, there can be mentioned: a method of mixing the powder particles and water and stirring with a stirrer, a method of kneading the powder particles and water with a kneader, a method of mixing the powder particles and water with a rotary-revolution stirrer, a method of spraying water on the powder particles, and a method of cleaning the cake of the powder particles with a pressure filter. As the kneader, various kneaders such as a batch kneader, a continuous kneader, and an extrusion kneader can be used.

[0077] The cleaning time is not particularly limited, and examples thereof include 1 second to 60 minutes, preferably 1 second to 45 minutes, more preferably 1 minute to 30 minutes, further preferably 3 minutes to 30 minutes, and particularly preferably 5 minutes to 30 minutes. The cleaning time can be 10 minutes to 30 minutes, or can be 5 minutes to 10 minutes.

[0078] The number of cleaning times is not particularly limited, and examples thereof include 1 to 10 times (cycles), preferably 1 time to 6 times (cycles), more preferably 1 time to 5 times (cycles), further preferably 1 time to 4 times (cycles), and particularly preferably 1 time to 3 times (cycles).

[0079] The amount of cleaning water is not particularly limited, and examples thereof include 0.1 parts by weight to 1000 parts by weight relative to 1 part by weight of the powder particles, preferably 1 part by weight to 500 parts by weight, 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 cleaning water relative to 1 part by weight of the agglomerate can be 15 parts by weight to 500 parts by weight, or can be 2 to 5 parts by weight. In addition, in the case of cleaning by kneading using a kneader, the amount of cleaning water can be reduced, which is therefore more preferable.

[0080] The temperature of the cleaning water is also not limited. For example, normal temperature cleaning water or heated warm water can be appropriately used. Since the cleaning effect of warm water is good, it is preferably to use the heated cleaning water. The temperature of the cleaning water is preferably a temperature lower than the glass transition temperature of the grafted part of the polymer particles (A). By setting the temperature of the cleaning water to be lower than the Tg of the grafted part of the polymer particles (A), it is possible to avoid the polymer particles (A) from sticking to each other and deteriorating the dispersibility. That is, it has the advantage that the dispersibility of the polymer particles (A) in the resin composition containing the obtained powder particles is more excellent. The temperature of the cleaning water can be, for example, 10°C to 100°C, preferably 15°C to 100°C, more preferably 20°C to 100°C, further preferably 40°C to 100°C, still further preferably 40°C to 80°C, and particularly preferably 40°C to 70°C. As the temperature of the cleaning water, it can be 15°C to 90°C, or can be 20°C to 85°C. In addition, as the temperature of the cleaning water, from the viewpoint of obtaining powder particles with excellent dispersibility in the matrix resin, it is preferably lower than 90°C, more preferably lower than 80°C, and further preferably lower than 70°C.

[0081] In addition, the method for removing the water after cleaning is not limited, and examples thereof include: discharging the cleaning water, vacuum filtration, oil-water separation, filter press, belt press, screw press, membrane separation, centrifugal dehydration, and squeeze dehydration, etc.

[0082] The object to be cleaned refers to all impurities contained in the powder particles, without any particular limitation. For example, in addition to inclusions from emulsifiers (e.g., phosphorus-based emulsifiers, sulfonic acid-based emulsifiers), when using the coagulant described below, inclusions from the coagulant can also be cited, etc.

[0083] (2-8. Drying process)

[0084] This manufacturing method may include a drying process for drying the powder particles obtained in the spraying process or the powder particles obtained in the cleaning process.

[0085] In the existing spray recovery technology and spray drying technology disclosed in Patent Documents 1 to 6, the latex droplets obtained in the spraying process need to be dried. For example, in the existing spray recovery technology and spray drying technology, latex is sprayed into a dryer with an inlet air temperature of 90°C to 160°C and an outlet air temperature of 40°C to 58°C to dry the latex droplets, or drying hot gas at 120°C to 180°C is brought into contact with the sprayed latex droplets for drying. It can be considered that through this drying, the water in the latex droplets evaporates, and polymer microparticles are obtained in the form of aggregates. It can be considered that in the prior art, in order to obtain powder, the drying process is essential.

[0086] In this manufacturing method, by including an impregnation process, polymer microparticles (A) can be recovered in the form of powder particles without including a drying process as disclosed in Patent Documents 1 to 6. That is, in this manufacturing method, the drying process is not an essential process, and this manufacturing method may not include a drying process. When this manufacturing method does not include a drying process, compared with the prior art, powder particles with a high moisture content can be obtained. Therefore, compared with the prior art, it has the advantage that the dispersibility of polymer microparticles (A) in the resin composition containing the obtained powder particles is more excellent.

[0087] (2-9. Polymer microparticles (A))

[0088] Polymer microparticles (A) are microparticles obtained by polymerization, and as long as they contain a graft copolymer having a graft portion, other compositions are not particularly limited. As polymer microparticles (A), for example, it is preferably a graft portion formed from a polymer having a structural unit containing at least one monomer source selected from aromatic vinyl monomers, vinyl cyanide monomers, and (meth)acrylate monomers as a structural unit.

[0089] (Graft portion)

[0090] In this specification, a polymer graft-bonded to any polymer is referred to as a graft portion. The graft portion is preferably a polymer containing a structural unit derived from one or more monomer sources selected from aromatic vinyl monomers, vinyl cyanide monomers, and (meth)acrylate monomers as a structural unit. Since the graft portion has the above constitution, it can play various roles. "Various roles" means, for example, (a) improving the compatibility between the polymer particles (A) and the thermosetting resin or thermoplastic resin, (b) improving the dispersibility of the polymer particles (A) in the thermosetting resin or thermoplastic resin which is the matrix resin (C) to be mixed, and (c) dispersing the polymer particles (A) in the state of primary particles in the resin composition containing the obtained powder particles, or its cured product or molded article, etc.

[0091] Specific examples of the aromatic vinyl monomer include styrene, α-methylstyrene, p-methylstyrene, and divinylbenzene, etc.

[0092] Specific examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile, etc.

[0093] Specific examples of the (meth)acrylate monomer include (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid butyl ester, (meth)acrylic acid hydroxyethyl ester, and (meth)acrylic acid hydroxybutyl ester, etc. In this specification, (meth)acrylate means acrylate and / or methacrylate.

[0094] One or more of the above monomers selected from aromatic vinyl monomers, vinyl cyanide monomers, and (meth)acrylate monomers can be used alone, or two or more can be used in combination.

[0095] The graft portion preferably contains a structural unit derived from a monomer having a reactive group as a structural unit. The monomer having a reactive group is preferably a monomer containing one or more reactive groups selected from epoxy group, oxetanyl group, hydroxyl group, amino group, imide group, carboxylic acid group, carboxylic anhydride group, cyclic ester, cyclic amide, benz oxazinyl group, and cyanate ester group, and more preferably a monomer containing one or more reactive groups selected from epoxy group, hydroxyl group, and carboxylic acid group. By the above constitution, the graft portion of the polymer particles (A) can be chemically bonded to the thermosetting resin or thermoplastic resin in the resin composition containing the obtained powder particles. Thus, in the resin composition containing the obtained powder particles, or its cured product or molded article, the good dispersion state of the polymer particles (A) can be maintained without causing the polymer particles (A) to aggregate.

[0096] Specific examples of the monomer having an epoxy group include glycidyl (meth)acrylate, glycidyl ether of 4-hydroxybutyl (meth)acrylate, and allyl glycidyl ether, etc.

[0097] Specific examples of the monomer having a hydroxyl group include, for example: hydroxy straight-chain alkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. (especially hydroxy straight-chain C1-6 alkyl (meth)acrylates); caprolactone-modified hydroxy (meth)acrylate; hydroxy branched-chain alkyl (meth)acrylates such as methyl α-(hydroxymethyl)acrylate, ethyl α-(hydroxymethyl)acrylate, etc.; mono(meth)acrylates of polyester diols (especially saturated polyester diols) obtained from dicarboxylic acids (such as phthalic acid) and diols (such as propylene glycol), etc., and hydroxy-containing (meth)acrylates.

[0098] Specific examples of the monomer having a carboxyl group include, for example: monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, and dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid, etc. As the monomer having a carboxyl group, the above-mentioned monocarboxylic acids can be preferably used.

[0099] The above-mentioned monomer containing a reactive group can be used alone or in combination of two or more.

[0100] In 100% by weight of the graft part, the graft part preferably contains 0.5 to 90% by weight of the structural unit derived from the monomer containing a reactive group, more preferably contains 1 to 50% by weight, further preferably contains 2 to 35% by weight, and particularly preferably contains 3 to 20% by weight. It has the following advantages: In 100% by weight of the graft part, (a) when the graft part contains 0.5% by weight or more of the structural unit derived from the monomer containing a reactive group, the resin composition containing the obtained powder particles can provide a cured product or a molded article having sufficient impact resistance, (b) when the graft part contains 90% by weight or less of the structural unit derived from the monomer containing a reactive group, the resin composition containing the obtained powder particles can provide a cured product or a molded article having sufficient impact resistance, and the storage stability of the resin composition becomes good.

[0101] The structural unit derived from the monomer containing a reactive group is preferably contained in the graft part, and more preferably contained only in the graft part.

[0102] The graft part can contain the structural unit derived from a polyfunctional monomer as a structural unit. When the graft part contains the structural unit derived from a polyfunctional monomer, it has the following advantages: (a) swelling of the polymer particles (A) can be prevented in the resin composition containing the obtained powder particles, (b) the operability of the resin composition tends to be good due to the decrease in the viscosity of the resin composition containing the obtained powder particles, and (c) the dispersibility of the polymer particles (A) in the thermosetting resin or thermoplastic resin is improved, etc.

[0103] In the case where the graft portion does not contain a structural unit derived from a polyfunctional monomer, compared with the case where the graft portion contains a structural unit derived from a polyfunctional monomer, a resin composition containing the obtained powder particles can provide a cured product or a molded article having more excellent toughness and impact resistance.

[0104] A polyfunctional monomer can be said to be a monomer having two or more radically polymerizable reactive groups in the same molecule. The above-mentioned radically polymerizable reactive group is preferably a carbon-carbon double bond. As the polyfunctional monomer, butadiene is not included, and examples thereof include (meth)acrylic acid allyl alkyl esters and (meth)acrylic acid allyloxyalkyl esters, such as (meth)acrylates having an ethylenic unsaturated double bond. As the monomer having two (meth)acrylic groups, examples include: ethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, and polyethylene glycol di(meth)acrylates. As the above-mentioned polyethylene glycol di(meth)acrylates, examples include: triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol(600) di(meth)acrylate, etc. In addition, as the monomer having three (meth)acrylic groups, examples include: alkoxylated trimethylolpropane tri(meth)acrylates, glycerol propoxylate tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate, etc. As the alkoxylated trimethylolpropane tri(meth)acrylates, examples include: trimethylolpropane tri(meth)acrylate, trimethylolpropane triethoxy tri(meth)acrylate, etc. In addition, as the monomer having four (meth)acrylic groups, examples include: pentaerythritol tetra(meth)acrylate, bis(trimethylolpropane) tetra(meth)acrylate, etc. In addition, as the monomer having five (meth)acrylic groups, examples include dipentaerythritol penta(meth)acrylate, etc. In addition, as the monomer having six (meth)acrylic groups, examples include bis(trimethylolpropane) hexa(meth)acrylate, etc. As the polyfunctional monomer, examples also include: diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, etc.

[0105] Among the above-mentioned polyfunctional monomers, as the polyfunctional monomers that can be preferably used for the polymerization of the graft portion, examples include: allyl methacrylate, ethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, and polyethylene glycol di(meth)acrylates. These polyfunctional monomers can be used alone or in combination of two or more.

[0106] In 100% by weight of the graft portion, the graft portion preferably contains 1 to 20% by weight of structural units derived from a polyfunctional monomer, more preferably 5 to 15% by weight.

[0107] For the graft portion, as structural units, in addition to the structural units derived from the above-mentioned monomers, structural units derived from other monomers may also be included.

[0108] In addition, the graft portion is preferably a polymer graft-bonded to an elastomer described later. In the case where the graft portion is a polymer graft-bonded to an elastomer described later, in the following description, "any polymer" can be replaced with "elastomer".

[0109] (Glass transition temperature of the graft portion)

[0110] The glass transition temperature of the graft portion (hereinafter sometimes 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, more preferably 80°C or lower, more preferably 70°C or lower, more preferably 60°C or lower, more preferably 50°C or lower, more preferably 40°C or lower, more preferably 30°C or lower, more preferably 20°C or lower, more preferably 10°C or lower, more preferably 0°C or lower, more preferably -20°C or lower, more preferably -40°C or lower, more preferably -45°C or lower, more preferably -50°C or lower, more preferably -55°C or lower, more preferably -60°C or lower, more preferably -65°C or lower, more preferably -70°C or lower, more preferably -75°C or lower, more preferably -80°C or lower, more preferably -85°C or lower, more preferably -90°C or lower, more preferably -95°C or lower, more preferably -100°C or lower, more preferably -105°C or lower, more preferably -110°C or lower, more preferably -115°C or lower, further preferably -120°C or lower, particularly preferably -125°C or lower. With this configuration, a powder having a low Tg can be obtained. As a result, a resin composition containing the obtained powder can provide a cured product or a molded article having excellent toughness.

[0111] 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, more preferably 70°C or higher, further preferably 90°C or higher, particularly preferably 110°C or lower. The powder having this configuration can provide a cured product or a molded article having a sufficient elastic modulus (rigidity).

[0112] The Tg of the graft portion can be determined according to the composition of the structural units contained in the graft portion, etc. In other words, the composition of the monomers used in the production (polymerization) of the graft portion can be changed to adjust the Tg of the obtained graft portion.

[0113] The Tg of the grafted part can be obtained by using a flat plate made of polymer microparticles and performing viscoelasticity measurement. Specifically, the Tg can be measured as follows: (1) For the flat plate made of polymer microparticles, dynamic viscoelasticity measurement is performed under tensile conditions using a dynamic viscoelasticity measurement device (for example, DVA-200 manufactured by IT Measurement and Control Co., Ltd.) to obtain a chart of tanδ; (2) For the obtained chart of tanδ, the peak temperature of tanδ is taken as the glass transition temperature. Here, when multiple peaks are obtained in the chart of tanδ, the highest peak temperature is taken as the glass transition temperature of the grafted part.

[0114] (Grafting ratio of the grafted part)

[0115] In one embodiment of the present invention, the polymer microparticle (A) is a polymer having the same composition as the grafted part and optionally has a polymer that is not grafted to any polymer. In the present specification, a polymer having the same composition as the grafted part and not grafted to any polymer is also referred to as a non-grafted polymer. This non-grafted polymer constitutes a part of the polymer microparticle (A) of one embodiment of the present invention. The above non-grafted polymer can be said to be a polymer that is not grafted to any polymer among the polymers produced in the polymerization of the grafted part.

[0116] In the present specification, the ratio of the polymer that is not grafted to any polymer among the polymers produced in the polymerization of the grafted part, that is, the ratio of the grafted part, is referred to as the grafting ratio. The grafting ratio can be said to be a value expressed as (weight of the grafted part) / {(weight of the grafted part)+(weight of the non-grafted polymer)}×100.

[0117] The grafting ratio of the grafted part is preferably 70% or more, more preferably 80% or more, and further preferably 90% or more. When the grafting ratio is 70% or more, there is an advantage that the viscosity of the resin composition containing the obtained powder particles does not become too high.

[0118] In this specification, the calculation method of the grafting rate is as described below. First, an aqueous latex containing polymer particles (A) is obtained, and then a powder of polymer particles (A) is obtained from the aqueous latex. As the method for obtaining the powder of polymer particles (A) from the aqueous latex, specifically, the following methods can be cited: (i) coagulating the polymer particles (A) in the above aqueous latex, (ii) dehydrating the obtained coagulum, and (iii) obtaining the powder of polymer particles (A) by further drying the coagulum. Next, 2 g of the powder of polymer particles (A) is dissolved in 50 mL of methyl ethyl ketone (hereinafter also referred to as MEK). Then, the obtained MEK solution is separated into a component soluble in MEK (MEK-soluble component) and a component insoluble in MEK (MEK-insoluble component). Specifically, using a centrifuge (manufactured by Hitachi Koki Co., Ltd., CP60E), the obtained MEK solution is centrifuged under the conditions of a rotational speed of 30,000 rpm for 1 hour to separate the solution into a MEK-soluble component and a MEK-insoluble component. Here, the centrifugation operation can be carried out in a total of 3 groups. Next, 20 mL of the concentrated MEK-soluble component is added to 200 mL of methanol and mixed. Then, an aqueous calcium chloride solution obtained 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 taken as the free polymer amount (FP amount). Then, the grafting rate can be calculated by the following formula.

[0119] Grafting rate (%) = 100 - [(FP amount) / {(FP amount)+(MEK-insoluble component)}] / (weight of the polymer in the grafted part)×10,000

[0120] It should be noted that the weight of the polymer other than the grafted part is the feeding amount of the monomers constituting the polymer other than the grafted part. The polymer other than the grafted part is an arbitrary polymer (for example, an elastomer). In addition, when the polymer particles (A) contain a surface-crosslinked polymer described later, the polymer other than the grafted part contains, for example, both an elastomer and a surface-crosslinked polymer. In addition, in the calculation of the grafting rate, the method for coagulating the polymer particles (A) is not particularly limited, and methods such as using a solvent, using a coagulant (also called a flocculant), and spraying the aqueous latex can be used. In addition, the weight of the polymer in the grafted part is the feeding amount of the monomers constituting the polymer in the grafted part.

[0121] (Modification example of the grafted part)

[0122] In one embodiment of the present invention, the grafting part may include only one type of grafting part having structural units of the same composition. In one embodiment of the present invention, the grafting part may also include multiple grafting parts having structural units of different compositions respectively.

[0123] In one embodiment of the present invention, the case where the grafting part includes multiple grafting parts will be described. In this case, the multiple grafting parts are respectively referred to as grafting part 1, grafting part 2, ···, grafting part n (n is an integer of 2 or more). The grafting part may include a mixture obtained by mixing grafting part 1, grafting part 2, ···, and grafting part n which are polymerized respectively. The grafting part may include a polymer obtained by successively polymerizing grafting part 1, grafting part 2, ···, and grafting part n respectively. In this way, successively polymerizing multiple polymers (grafting parts) respectively is also called multi-step polymerization. The polymer obtained by subjecting multiple grafting parts to multi-step polymerization is also called a multi-step polymerization grafting part. The manufacturing method of the multi-step polymerization grafting part will be described in detail later.

[0124] When the grafting part includes multiple grafting parts, not all of these multiple grafting parts may be graft-bonded to any polymer. As long as at least a part of at least one type of grafting part is graft-bonded to any polymer, other types (other multiple) of grafting parts may be graft-bonded to the grafting part graft-bonded to any polymer. In addition, when the grafting part includes multiple grafting parts, it may be a polymer having the same constitution as the multiple grafting parts, and optionally multiple polymers (multiple non-grafted polymers) that are not graft-bonded to any polymer.

[0125] The multi-step polymerization grafting part including grafting part 1, grafting part 2, ···, and grafting part n will be described. In this multi-step polymerization grafting part, grafting part n may cover at least a part of grafting part n-1 or may cover the whole of grafting part n-1 . In this multi-step polymerization grafting part, sometimes a part of grafting part n enters the inside of grafting part n-1 .

[0126] In the multi-step polymerization grafting part, multiple grafting parts can each have a layer structure. For example, when the multi-step polymerization grafting part includes grafting part 1, grafting part 2, and grafting part 3, taking grafting part 1 as the innermost layer among the grafting parts, having a layer of grafting part 2 outside grafting part 1, and further having a layer of grafting part 3 as the outermost layer outside the layer of grafting part 2 is also one mode of the present invention. In this way, a multi-step polymerization grafting part in which multiple grafting parts each have a layer structure can also be said to be a multi-layer grafting part. That is, in one embodiment of the present invention, the grafting part can include a mixture of multiple types of grafting parts, a multi-step polymerization grafting part, and / or a multi-layer grafting part.

[0127] When any polymer and the grafting part are sequentially polymerized in the production of the polymer particles (A), in the obtained polymer particles (A), at least a part of the grafting part can coat at least a part of any polymer. For the sequential polymerization of any polymer and the grafting part, in other words, it can also be said to be the multi-step polymerization of any polymer and the grafting part. The polymer particles (A) obtained by the multi-step polymerization of any polymer and the grafting part can be called multi-step polymers.

[0128] When the polymer particles (A) are multi-step polymers, the grafting part can coat at least a part of any polymer or can coat the whole of any polymer. When the polymer particles (A) are multi-step polymers, sometimes a part of the grafting part enters the inside of any polymer.

[0129] When the polymer particles (A) are multi-step polymers, any polymer and the grafting part can have a layer structure. For example, taking any polymer as the innermost layer (also called the core layer) and having a layer of the grafting part as the outermost layer (also called the shell layer) outside any polymer is also one mode of the present invention. The structure with any polymer as the core layer and the grafting part as the shell layer is also called a core-shell structure. In this way, the polymer particles (A) in which any polymer and the grafting part have a layer structure (core-shell structure) are also called multi-layer polymers or core-shell polymers. That is, in one embodiment of the present invention, the polymer particles (A) can be multi-step polymers and / or multi-layer polymers or core-shell polymers. Among them, as long as there is a grafting part, the polymer particles (A) are not limited to the above-mentioned constitution.

[0130] Preferably, at least a part of the grafting part coats at least a part of any polymer. In other words, at least a part of the grafting part preferably exists on the outermost side of the polymer particles (A).

[0131] (Elastomer)

[0132] The polymer fine particles (A) preferably further have an elastomer. That is, the polymer fine particles (A) preferably contain a rubber-containing graft copolymer having an elastomer and a graft portion graft-bonded to the elastomer, and more preferably a rubber-containing graft copolymer. Hereinafter, a case where the polymer fine particles (A) are a rubber-containing graft copolymer will be taken as an example to describe an embodiment of the present invention.

[0133] The elastomer preferably contains one or more selected from diene rubbers, (meth)acrylate rubbers, and polysiloxane rubber elastomers. The elastomer can also be referred to as rubber particles.

[0134] The case where the elastomer contains a diene rubber (Case A) will be described. In Case A, the resin composition containing the obtained powder can provide a cured product or a molded article excellent in toughness and impact resistance.

[0135] The above diene rubber is an elastomer containing a structural unit derived from a diene monomer as a structural unit. The above diene monomer can also be referred to as a conjugated diene monomer. In Case A, for the diene rubber, in 100% by weight of the structural units, it can contain 50 to 100% by weight of the structural units derived from the diene monomer, and contain 0 to 50% by weight of the structural units derived from vinyl monomers other than the diene monomers that can copolymerize with the diene monomer. In Case A, the diene rubber can contain a structural unit derived from a (meth)acrylate monomer as a structural unit in an amount less than that of the structural unit derived from the diene monomer.

[0136] Examples of the diene monomer include 1,3-butadiene, isoprene, 2-chloro-1,3-butadiene, 2-methyl-1,3-butadiene, etc. These diene monomers can be used alone or in combination of two or more.

[0137] As vinyl monomers other than diene monomers that can copolymerize with diene monomers (hereinafter, also referred to as vinyl monomer A), examples include: vinyl aromatic hydrocarbons such as styrene, α-methylstyrene, monochlorostyrene, and dichlorostyrene; vinyl carboxylic acids such as acrylic acid and methacrylic acid; vinyl cyanides such as acrylonitrile and methacrylonitrile; vinyl halides such as vinyl chloride, vinyl bromide, and chloroprene; vinyl acetate; olefins such as ethylene, propylene, butene, and isobutene; polyfunctional monomers such as diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, and divinylbenzene. The above-mentioned vinyl monomers other than diene monomers can be used alone or in combination of two or more. Among the above-mentioned vinyl monomers other than diene monomers, styrene is particularly preferred. It should be noted that in the diene rubber of Case A, the structural unit derived from the vinyl monomer other than the diene monomer is an optional component. In Case A, the diene rubber can be composed only of the structural unit derived from the diene monomer.

[0138] In Case A, as the diene rubber, a butadiene rubber (also referred to as polybutadiene rubber) formed from the structural unit derived from 1,3-butadiene or a butadiene-styrene rubber (also referred to as polystyrene-butadiene), which is a copolymer of 1,3-butadiene and styrene, is preferred, and a butadiene rubber is more preferred. With the above configuration, the desired effect of the polymer particles (A) containing the diene rubber can be further exerted. In addition, from the viewpoint of being able to improve the transparency of the obtained cured product or molded article by adjusting the refractive index, a butadiene-styrene rubber is more preferred.

[0139] The case where the elastomer contains a (meth)acrylate rubber (Case B) will be described. In Case B, an elastomer with a wide range of polymers can be designed by combining various monomers.

[0140] The above-mentioned (meth)acrylate rubber is an elastomer containing the structural unit derived from the (meth)acrylate monomer as the structural unit. In Case B, for the (meth)acrylate rubber, in 100% by weight of the structural unit, it can contain 50 to 100% by weight of the structural unit derived from the (meth)acrylate monomer and 0 to 50% by weight of the structural unit derived from the vinyl monomer other than the (meth)acrylate monomer that can copolymerize with the (meth)acrylate monomer. In Case B, the (meth)acrylate rubber can contain the structural unit derived from the diene monomer in an amount less than that of the structural unit derived from the (meth)acrylate monomer.

[0141] Examples of the (meth)acrylate monomers include, for example, (meth)acrylate alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, and docosyl (meth)acrylate; (meth)acrylate esters containing an aromatic ring such as phenoxyethyl (meth)acrylate and benzyl (meth)acrylate; (meth)acrylate hydroxyalkyl esters such as 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate; (meth)acrylate glycidyl esters such as glycidyl (meth)acrylate and glycidyl alkyl (meth)acrylate; (meth)acrylate alkoxyalkyl esters; (meth)acrylate allyl alkyl esters such as allyl (meth)acrylate and allyl alkyl (meth)acrylate; and polyfunctional (meth)acrylate esters such as diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and tetraethylene glycol di(meth)acrylate. These (meth)acrylate monomers may be used alone or in combination of two or more. Among these (meth)acrylate monomers, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate are particularly preferred.

[0142] Examples of the vinyl monomers other than the (meth)acrylate monomers capable of copolymerizing with the (meth)acrylate monomers (hereinafter, also referred to as vinyl monomers other than the (meth)acrylate monomers) include the monomers listed in the above vinyl monomer A. The vinyl monomers other than the (meth)acrylate monomers may be used alone or in combination of two or more. Among the vinyl monomers other than the (meth)acrylate monomers, styrene is particularly preferred. It should be noted that in the (meth)acrylate rubber in Case B, the structural unit derived from the vinyl monomer other than the (meth)acrylate monomer is an optional component. In Case B, the (meth)acrylate rubber may be composed only of the structural unit derived from the (meth)acrylate monomer.

[0143] The case where the elastomer contains a polysiloxane rubber elastomer (Case C) will be described. In Case C, the resin composition containing the obtained powder particles can provide a cured product or a molded article having sufficient heat resistance and excellent impact resistance at low temperatures.

[0144] As polysiloxane rubber - like elastomers, for example, the following can be cited: (a) Polysiloxane - type polymers composed of alkyldisubstituted or aryldisubstituted siloxane units such as dimethylsiloxaneoxy, diethylsiloxaneoxy, methylphenylsiloxaneoxy, diphenylsiloxaneoxy, dimethylsiloxaneoxy - diphenylsiloxaneoxy; (b) Polysiloxane - type polymers composed of alkyl - or aryl - monosubstituted siloxane units such as organohydrosiloxaneoxy in which a part of the alkyl groups in the side chain is substituted with hydrogen atoms. These polysiloxane - type polymers can be used alone or in combination of two or more. Among these polysiloxane - type polymers, (a) from the viewpoint that the resin composition containing the obtained powder particles can provide a cured product or a molded article with excellent heat resistance, a polymer composed of dimethylsiloxaneoxy units, methylphenylsiloxaneoxy units, and / or dimethylsiloxaneoxy - diphenylsiloxaneoxy units is preferred; (b) from the viewpoints of easy availability and economy, a polymer composed of dimethylsiloxaneoxy units is most preferred.

[0145] In case C, in 100% by weight of the elastomer contained in the polymer particle (A), the polymer particle (A) preferably contains 80% by weight or more of the polysiloxane rubber - like elastomer, more preferably 90% by weight or more. With the above - mentioned constitution, the resin composition containing the obtained powder particles can provide a cured product or a molded article with excellent heat resistance.

[0146] The elastomer may further contain elastomers other than diene - type rubbers, (meth)acrylate - type rubbers, and polysiloxane rubber - like elastomers. As elastomers other than diene - type rubbers, (meth)acrylate - type rubbers, and polysiloxane rubber - like elastomers, for example, natural rubber can be cited.

[0147] (Cross - linked structure of the elastomer)

[0148] From the viewpoint of maintaining the dispersion stability of the polymer particle (A) in the thermosetting resin or thermoplastic resin, it is preferred to introduce a cross - linked structure into the elastomer. As a method for introducing a cross - linked structure into the elastomer, a commonly used method can be adopted. For example, the following methods can be cited. That is, in the production of the elastomer, a method of mixing a polyfunctional monomer and / or a cross - linkable monomer such as a mercapto - containing compound in the monomers capable of forming the elastomer and then carrying out polymerization can be cited. In this specification, the production of polymers such as elastomers is also referred to as polymerization into polymers.

[0149] In addition, as a method for introducing a crosslinked structure into a polysiloxane rubber-based elastomer, the following methods can be cited: (a) a method in which a polyfunctional alkoxysilane compound is partially used in combination with other materials during the polymerization of the polysiloxane rubber-based elastomer; (b) a method in which a reactive group such as a vinyl-reactive group or a mercapto group is introduced into the polysiloxane rubber-based elastomer, and then a vinyl-polymerizable monomer or an organic peroxide is added to carry out a radical reaction; or (c) a method in which a crosslinkable monomer such as a polyfunctional monomer and / or a mercapto group-containing compound is mixed with other materials during the polymerization of the polysiloxane rubber-based elastomer, and then polymerization is carried out, etc.

[0150] As the polyfunctional monomer, the polyfunctional monomers exemplified in the above (graft portion) item can be cited.

[0151] Examples of the mercapto group-containing compound include: alkyl-substituted thiols, allyl-substituted thiols, aryl-substituted thiols, hydroxy-substituted thiols, alkoxy-substituted thiols, cyano-substituted thiols, amino-substituted thiols, silyl-substituted thiols, acid group-substituted thiols, halogen-substituted thiols, and acyl-substituted thiols, etc. As the alkyl-substituted thiol, an alkyl-substituted thiol having 1 to 20 carbon atoms is preferred, and an alkyl-substituted thiol having 1 to 10 carbon atoms is more preferred. As the aryl-substituted thiol, a phenyl-substituted thiol is preferred. As the alkoxy-substituted thiol, an alkoxy-substituted thiol having 1 to 20 carbon atoms is preferred, and an alkoxy-substituted thiol having 1 to 10 carbon atoms is more preferred. As the acid group-substituted thiol, an alkyl-substituted thiol having 1 to 10 carbon atoms having a carboxyl group or an aryl-substituted thiol having 1 to 12 carbon atoms having a carboxyl group is preferred.

[0152] (Glass transition temperature of the elastomer)

[0153] From the viewpoint of obtaining a cured product or a molded article having excellent toughness, the glass transition temperature (hereinafter sometimes simply referred to as "Tg") of the elastomer is preferably 80°C or lower, more preferably 70°C or lower, still more preferably 60°C or lower, still more preferably 50°C or lower, still more preferably 40°C or lower, still more preferably 30°C or lower, still more preferably 20°C or lower, still more preferably 10°C or lower, still more preferably 0°C or lower, still more preferably -20°C or lower, still more preferably -40°C or lower, still more preferably -45°C or lower, still more preferably -50°C or lower, still more preferably -55°C or lower, still more preferably -60°C or lower, still more preferably -65°C or lower, still more preferably -70°C or lower, still more preferably -75°C or lower, still more preferably -80°C or lower, still more preferably -85°C or lower, still more preferably -90°C or lower, still more preferably -95°C or lower, still more preferably -100°C or lower, still more preferably -105°C or lower, still more preferably -110°C or lower, still more preferably -115°C or lower, further preferably -120°C or lower, and particularly preferably -125°C or lower. With this configuration, a powder or granule having a low Tg can be obtained. As a result, a resin composition containing the obtained powder or granule can provide a cured product or a molded article having excellent toughness.

[0154] On the other hand, a decrease in the elastic modulus (rigidity) of the obtained cured product or molded article can be suppressed, that is, a cured product or a molded article having a sufficient elastic modulus (rigidity) can be obtained. Therefore, the Tg of the elastomer is preferably higher than 0°C, 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.

[0155] The Tg of the elastomer can be determined according to the composition of the structural units contained in the elastomer and the like. In other words, the Tg of the obtained elastomer can be adjusted by changing the composition of the monomers used in the production (polymerization) of the elastomer.

[0156] The Tg of the elastomer can be obtained by using a flat plate made of the elastomer and performing viscoelasticity measurement. Specifically, the Tg can be measured as follows: (1) For a flat plate formed of the elastomer, dynamic viscoelasticity measurement is performed under tensile conditions using a dynamic viscoelasticity measurement device (for example, DVA-200 manufactured by IT Measurement and Control Co., Ltd.) to obtain a graph of tanδ; (2) For the obtained graph of tanδ, the peak temperature of tanδ is taken as the glass transition temperature. Here, when multiple peaks are obtained in the graph of tanδ, the lowest peak temperature is taken as the glass transition temperature of the elastomer.

[0157] Here, a monomer group that provides a homopolymer having a Tg greater than 0 °C when forming a homopolymer formed by polymerizing only one kind of monomer is defined as monomer group a. Additionally, a monomer group that provides a homopolymer having a Tg less than 0 °C when forming a homopolymer formed by polymerizing only one kind of monomer is defined as monomer group b. An elastomer containing 50 to 100% by weight (more preferably 65 to 99% by weight) of structural units derived from at least one monomer selected from monomer group a and 0 to 50% by weight (more preferably 1 to 35% by weight) of structural units derived from at least one monomer selected from monomer group b is defined as elastomer X. The Tg of elastomer X is also greater than 0 °C. Additionally, when the elastomer contains elastomer X, a resin composition containing the resulting powder particles can provide a cured product or molded article having sufficient rigidity.

[0158] When the Tg of the elastomer is greater than 0 °C, it is also preferable to introduce a crosslinked structure into the elastomer. As a method for introducing the crosslinked structure, the above-described methods can be cited.

[0159] Examples of the monomers that can be included in the above monomer group a are not limited to the following, and include, for example: unsubstituted vinyl aromatic compounds such as styrene and 2-vinylnaphthalene; vinyl-substituted aromatic compounds such as α-methylstyrene; cycloalkylated vinyl aromatic compounds such as 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,5-dimethylstyrene, and 2,4,6-trimethylstyrene; cycloalkoxylated vinyl aromatic compounds such as 4-methoxystyrene and 4-ethoxystyrene; cyclohalo vinyl aromatic compounds such as 2-chlorostyrene and 3-chlorostyrene; cycloester-substituted vinyl aromatic compounds such as 4-acetoxystyrene; cyclo-hydroxylated vinyl aromatic compounds such as 4-hydroxystyrene; vinyl esters such as vinyl benzoate and vinyl cyclohexanecarboxylate; halo vinyls such as vinyl chloride; aromatic monomers such as acenaphthylene and indene; alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, and isopropyl methacrylate; aromatic methacrylates such as phenyl methacrylate; methacrylates such as isobornyl methacrylate and trimethylsilyl methacrylate; methacrylic monomers containing methacrylic acid derivatives such as methacrylonitrile; certain acrylates such as isobornyl acrylate and tert-butyl acrylate; acrylic monomers containing acrylic acid derivatives such as acrylonitrile. Additionally, examples of the monomers that can be included in the above monomer group a include monomers that can provide a homopolymer having a Tg of 120 °C or higher when forming a homopolymer, such as acrylamide, isopropylacrylamide, N-vinylpyrrolidone, isobornyl methacrylate, dicyclopentyl methacrylate, 2-methyl-2-adamantyl methacrylate, 1-adamantyl acrylate, and 1-adamantyl methacrylate. These monomers a can be used alone or in combination of two or more.

[0160] As the above monomer b, examples thereof include ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, octyl (meth)acrylate, dodecyl (meth)acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, etc. These monomer bs may be used alone or in combination of two or more. Among these monomer bs, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate are particularly preferred.

[0161] (Volume average particle diameter of the elastomer)

[0162] The volume average particle diameter of the elastomer is preferably 0.03 μm to 50.00 μm, more preferably 0.05 μm to 10.00 μm, still more preferably 0.08 μm to 2.00 μm, further preferably 0.10 μm to 1.00 μm, still further preferably 0.10 μm to 0.80 μm, and particularly preferably 0.10 μm to 0.50 μm. When the volume average particle diameter of the elastomer is (a) 0.03 μm or more, an elastomer having a desired volume average particle diameter can be stably obtained. When (b) it is 50.00 μm or less, the heat resistance and impact resistance of the obtained cured product or molded article become good. For the volume average particle diameter of the elastomer, an aqueous latex containing the elastomer can be used as a sample, and measured using a dynamic light scattering type particle size distribution measuring device, etc. The volume average particle diameter of the elastomer is described in detail in the following examples.

[0163] (Ratio of the elastomer)

[0164] Assuming the total amount of the polymer particles (A) is 100% by weight, the proportion of the elastomer in the polymer particles (A) is preferably 40 to 97% by weight, more preferably 60 to 95% by weight, and still more preferably 70 to 93% by weight. When the above proportion of the elastomer is (a) 40% by weight or more, the resin composition containing the obtained powder particles can provide a cured product or molded article having excellent toughness and impact resistance. When (b) it is 97% by weight or less, the polymer particles (A) are not easily aggregated. Therefore, the resin composition containing the obtained powder particles does not become highly viscous, and as a result, the resin composition has excellent operability.

[0165] (Gel content of the elastomer)

[0166] The elastomer is preferably an elastomer that can swell in a suitable solvent but is substantially insoluble. The elastomer is preferably unnecessary for the thermosetting resin or thermoplastic resin to be used.

[0167] The gel content of the elastomer is preferably 60% by weight or more, more preferably 80% by weight or more, still more preferably 90% by weight or more, and particularly preferably 95% by weight or more. When the gel content of the elastomer is within the above range, the resin composition containing the obtained powder particles can provide a cured product or a molded article having excellent toughness.

[0168] In this specification, the calculation method of the gel content is as described below. First, an aqueous latex containing polymer particles (A) is obtained, and then powder particles of polymer particles (A) are obtained from the aqueous latex. As the method for obtaining powder particles of polymer particles (A) from the aqueous latex, there is no particular limitation, and examples thereof include: (i) coagulating the polymer particles (A) in the aqueous latex, (ii) dehydrating the obtained coagulum, and (iii) further drying the coagulum to obtain powder particles of polymer particles (A). Next, 2.0 g of the powder particles of polymer particles (A) are dissolved in 50 mL of methyl ethyl ketone. Then, the obtained MEK solution is separated into a component soluble in MEK (MEK-soluble component) and a component insoluble in MEK (MEK-insoluble component). Specifically, using a centrifuge (manufactured by Hitachi Koki Co., Ltd., CP60E) under the conditions of a rotation speed of 30,000 rpm for 1 hour, the obtained MEK solution is centrifuged to separate the solution into a MEK-soluble component and a MEK-insoluble component. Here, the centrifugation operation is carried out in a total of 3 groups. The weights of the obtained MEK-soluble component and MEK-insoluble component are measured, and the gel content is calculated by the following formula.

[0169] Gel content (%) = (weight of MEK-insoluble component) / {(weight of MEK-insoluble component)+(weight of MEK-soluble component)}×100.

[0170] (Modified example of elastomer)

[0171] In one embodiment of the present invention, the elastomer may contain only one type of elastomer selected from diene rubbers, (meth)acrylate rubbers, and polysiloxane rubber elastomers and having structural units of the same composition. In one embodiment of the present invention, the elastomer may also contain a plurality of elastomers having structural units of different compositions.

[0172] In one embodiment of the present invention, the case where the elastomer contains a plurality of elastomers will be described. In this case, the plurality of elastomers are respectively referred to as elastomer 1, elastomer 2, ···, and elastomer n . Here, n is an integer of 2 or more. The elastomer may contain elastomer 1, elastomer 2, ···, and elastomer respectively polymerized by themselves nA mixture obtained by mixing. The elastomer may include elastomer 1, elastomer 2, ···, and elastomer n A polymer obtained by multi-step polymerization. A polymer obtained by multi-step polymerization of a plurality of elastomers is also referred to as a multi-step polymerization elastomer. The manufacturing method of the multi-step polymerization elastomer will be described in detail later.

[0173] Regarding the multi-step polymerization elastomer containing elastomer 1, elastomer 2, ···, and elastomer n will be described. In this multi-step polymerization elastomer, elastomer n may coat at least a part of elastomer n-1 or may coat the whole of elastomer n-1 . In this multi-step polymerization elastomer, sometimes a part of elastomer n enters the inside of elastomer n-1 .

[0174] In the multi-step polymerization elastomer, the plurality of elastomers may each have a layer structure. For example, when the multi-step polymerization elastomer includes elastomer 1, elastomer 2, and elastomer 3, a mode in which elastomer 1 is the innermost layer, a layer of elastomer 2 exists outside elastomer 1, and a layer of elastomer 3 further exists outside the layer of elastomer 2 as the outermost layer of the elastomers is also one mode of the present invention. Thus, a multi-step polymerization elastomer in which the plurality of elastomers each have a layer structure can also be said to be a multilayer elastomer. That is, in one embodiment of the present invention, the elastomer may include a mixture of a plurality of elastomers, a multi-step polymerization elastomer, and / or a multilayer elastomer.

[0175] (Surface crosslinked polymer)

[0176] In addition to the graft portion and optionally the above-mentioned elastomer, the polymer particle (A) preferably further has a surface crosslinked polymer. Hereinafter, a case where the polymer particle (A) has a surface crosslinked polymer in addition to the elastomer and the graft portion will be taken as an example to describe the surface crosslinked polymer. With the above configuration, (a) in the production of the polymer particle (A), the anti-adhesion property can be improved, and (b) the dispersibility of the polymer particle (A) in the thermosetting resin or the thermoplastic resin becomes better. The reason is not particularly limited and can be speculated as follows: The surface crosslinked polymer coats at least a part of, for example, the elastomer, and the exposure of the elastomer portion of the polymer particle (A) is reduced. As a result, the elastomers are not easily adhered to each other, and thus the dispersibility of the polymer particle (A) is improved.

[0177] In the case where the polymer particles (A) have a surface-crosslinked polymer, the following effects can be further obtained: (a) an effect of reducing the viscosity of a resin composition containing the resulting powder, (b) an effect of increasing the crosslinking density of an elastomer, and (c) an effect of increasing the grafting efficiency of a graft portion. The crosslinking density of an elastomer refers to the degree of the number of crosslinked structures in the whole elastomer.

[0178] The surface-crosslinked polymer is formed from a polymer containing 30 to 100% by weight of structural units derived from a polyfunctional monomer and 0 to 70% by weight of structural units derived from other vinyl monomers as structural units, and the total thereof is 100% by weight.

[0179] As the polyfunctional monomer that can be used in the polymerization of the surface-crosslinked polymer, the same monomers as the above-mentioned polyfunctional monomers can be cited. Among these polyfunctional monomers, the polyfunctional monomers that can be preferably used in the polymerization of the surface-crosslinked polymer include: allyl methacrylate, ethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, and polyethylene glycol di(meth)acrylates. These polyfunctional monomers can be used alone or in combination of two or more.

[0180] The polymer particles (A) may contain a surface-crosslinked polymer formed by polymerization independently of the polymerization of the rubber-containing graft copolymer, or may contain a surface-crosslinked polymer formed by polymerization together with the rubber-containing graft copolymer. The polymer particles (A) may be a multi-step polymer obtained by multi-step polymerization of an elastomer, a surface-crosslinked polymer, and a graft portion in this order. In any of these methods, the surface-crosslinked polymer may cover at least a part of the elastomer.

[0181] The surface-crosslinked polymer can also be regarded as a part of the elastomer. In other words, the surface-crosslinked polymer can also be regarded as a part of the rubber-containing graft copolymer, and can also be called a surface-crosslinked polymerization portion. In the case where the polymer particles (A) contain a surface-crosslinked polymer, the graft portion (a) can be graft-bonded to an elastomer other than the surface-crosslinked polymer, (b) can also be graft-bonded to the surface-crosslinked polymer, and (c) can further be graft-bonded to both an elastomer other than the surface-crosslinked polymer and the surface-crosslinked polymer. In the case where the polymer particles (A) contain a surface-crosslinked polymer, the above-mentioned volume-average particle diameter of the elastomer refers to the volume-average particle diameter of the elastomer containing the surface-crosslinked polymer.

[0182] The case where the polymer particle (A) is a multi-step polymer obtained by multi-step polymerization of an elastomer, a surface-crosslinked polymer, and a graft portion in this order (Case D) will be described. In Case D, the surface-crosslinked polymer may coat a part of the elastomer or may coat the entire elastomer. In Case D, a part of the surface-crosslinked polymer may enter the inside of the elastomer. In Case D, the graft portion may coat a part of the surface-crosslinked polymer or may coat the entire 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 elastomer, the surface-crosslinked polymer, and the graft portion may have a layer structure. For example, a mode in which the elastomer is the innermost layer (core layer), a layer of the surface-crosslinked polymer exists outside the elastomer as the intermediate layer, and a layer of the graft portion exists outside the surface-crosslinked polymer as the outermost layer (shell layer) is also one mode of the present invention.

[0183] (Volume average particle diameter (Mv) of the polymer particle (A))

[0184] From the viewpoint that the resin composition containing the obtained powder has a desired viscosity and is highly stable, the volume average particle diameter (Mv) of the polymer particle (A) is preferably 0.03 μm to 50.00 μm, more preferably 0.05 μm to 10.00 μm, still more preferably 0.08 μm to 2.00 μm, further preferably 0.10 μm to 1.00 μm, still further preferably 0.10 μm to 0.80 μm, and particularly preferably 0.10 μm to 0.50 μm. From the viewpoint that the dispersibility of the polymer particle (A) in the thermosetting resin or the thermoplastic resin becomes good, the volume average particle diameter (Mv) of the polymer particle (A) is further preferably 0.1 to 0.5 μm. It should be noted that in this specification, unless otherwise specified, the "volume average particle diameter (Mv) of the polymer particle (A)" refers to the volume average particle diameter of the primary particles of the polymer particle (A). For the volume average particle diameter of the polymer particle (A), an aqueous latex containing the polymer particle (A) can be used as a sample, and measured using a dynamic light scattering type particle size distribution measuring device or the like. The volume average particle diameter of the polymer particle (A) will be described in detail in the following examples. Regarding the volume average particle diameter of the polymer particle (A), the cured product of the resin composition containing the obtained powder can be cut and the cut surface can be photographed using an electron microscope or the like, and measured using the obtained photographed data (photographed image).

[0185] From the viewpoint that the resin composition containing the obtained powder has a low viscosity and is easy to operate, the number distribution of the particle diameters of the polymer particle (A) in the thermosetting resin or the thermoplastic resin preferably has a half-peak width of 0.5 times or more and 1 time or less of the volume average particle diameter.

[0186] (2-10. Method for manufacturing polymer particles (A) (latex manufacturing process))

[0187] In one embodiment of the present invention, as a pre-stage of the above impregnation process, it may include a manufacturing process of polymer particles (A), particularly a latex manufacturing process for manufacturing a latex containing polymer particles (A). Latex refers to aqueous latex.

[0188] For example, polymer particles (A) can be manufactured by polymerizing any polymer and then graft-polymerizing a polymer constituting a graft portion in the presence of the polymer. Hereinafter, an example of the manufacturing method of polymer particles (A) will be described by taking the case of manufacturing polymer particles (A) by polymerizing an elastomer and then graft-polymerizing a polymer constituting a graft portion in the presence of the elastomer as an example.

[0189] Polymer particles (A) can be manufactured by known methods such as emulsion polymerization, suspension polymerization, minisuspension polymerization, etc. Specifically, the polymerization of the elastomer, the polymerization of the graft portion (graft polymerization), and the polymerization of the surface crosslinked polymer in polymer particles (A) can be manufactured by known methods such as emulsion polymerization, suspension polymerization, minisuspension polymerization, etc. Among them, particularly from the viewpoints of easy composition design of polymer particles (A), easy industrial production, and easy availability of an aqueous latex of polymer particles (A) suitable for use in the manufacture of powder particles, emulsion polymerization is preferred as the manufacturing method of polymer particles (A). Hereinafter, the manufacturing methods of the elastomer, the graft portion, and the optional surface crosslinked polymer that can be contained in polymer particles (A) will be described.

[0190] (Manufacturing method of elastomer)

[0191] Consider the case where the elastomer contains at least one or more selected from diene rubbers and (meth)acrylate rubbers. In this case, the elastomer can be manufactured by methods such as emulsion polymerization, suspension polymerization, minisuspension polymerization, etc., and as its manufacturing method, for example, the method described in WO2005 / 028546 can be used.

[0192] Consider the case where the elastomer contains a polysiloxane rubber-based elastomer. In this case, the elastomer can be manufactured by methods such as emulsion polymerization, suspension polymerization, minisuspension polymerization, etc., and as its manufacturing method, for example, the method described in WO2006 / 070664 can be used.

[0193] The manufacturing method of the elastomer in the case where the elastomer contains a plurality of elastomers (for example, elastomer 1, elastomer 2, ···, elastomer n ) will be described. In this case, elastomer 1, elastomer 2, ···, elastomer nThey can be polymerized respectively by the above methods and then mixed to produce an elastomer having a plurality of elastomers. Alternatively, elastomer 1, elastomer 2, ···, elastomer n can be polymerized step by step successively to produce an elastomer having a plurality of elastomers.

[0194] The multi-step polymerization of the elastomer will be specifically described. For example, (1) polymerize elastomer 1 to obtain elastomer 1; (2) then, polymerize elastomer 2 in the presence of elastomer 1 to obtain a two-step elastomer 1+2 ; (3) then, polymerize elastomer 3 in the presence of elastomer 1+2 to obtain a three-step elastomer 1+2+3 ; (4) hereinafter, after performing similarly, polymerize elastomer 1+2+···+(n-1) in the presence of elastomer n to obtain a multi-step polymerized elastomer 1+2+···+n .

[0195] (Manufacturing method of graft part)

[0196] The graft part can be formed by polymerizing a monomer for forming the graft part by, for example, using a known radical polymerization. When obtaining (a) an elastomer or (b) a polymer particle precursor containing an elastomer and a surface crosslinked polymer in the form of an aqueous latex, the polymerization of the graft part is preferably carried out by an emulsion polymerization method. The graft part can be manufactured according to the method described in, for example, WO2005 / 028546.

[0197] The manufacturing method of the graft part when the graft part contains a plurality of graft parts (for example, graft part 1, graft part 2, ···, graft part n ) will be described. In this case, graft part 1, graft part 2, ···, graft part n can be polymerized respectively by the above methods and then mixed to produce a graft part having a plurality of graft parts. Alternatively, graft part 1, graft part 2, ···, graft part n can be polymerized step by step successively to produce a graft part having a plurality of graft parts.

[0198] The multi-step polymerization of the graft part will be specifically described. For example, (1) polymerize graft part 1 to obtain graft part 1; (2) then, polymerize graft part 2 in the presence of graft part 1 to obtain a two-step graft part 1+2 ; (3) then, polymerize graft part 3 in the presence of graft part 1+2 to obtain a three-step graft part 1+2+3 ; (4) hereinafter, after performing similarly, polymerize graft part 1+2+···+(n-1) in the presence of graft part n to obtain a multi-step polymerized graft part 1+2+···+n .

[0199] In the case where the grafting part contains a plurality of grafting parts, after polymerizing the grafting parts having a plurality of grafting parts, these grafting parts can be graft-polymerized onto the elastomer to produce the polymer particles (A). In the presence of the elastomer, a plurality of polymers constituting the plurality of grafting parts can be successively graft-polymerized onto the elastomer in multiple stages to produce the polymer particles (A).

[0200] (Method for producing surface-crosslinked polymer)

[0201] The surface-crosslinked polymer can be formed by polymerizing the monomers used for the formation of the surface-crosslinked polymer by known radical polymerization. In the case where the elastomer is obtained in the form of an aqueous latex, the polymerization of the surface-crosslinked polymer is preferably carried out by emulsion polymerization.

[0202] As a method for producing the polymer particles (A), in the case of using emulsion polymerization, known emulsifiers (dispersants) can be used in the production of the polymer particles (A).

[0203] Examples of the emulsifier include: (a) anionic emulsifiers such as the acids exemplified below, alkali metal salts of the acids, or ammonium salts of the acids, (b) nonionic emulsifiers such as alkyl- or aryl-substituted polyethylene glycols, (c) polyvinyl alcohol, alkyl-substituted cellulose, polyvinylpyrrolidone, polyacrylic acid derivatives, etc. Examples of the above acids include: (a1) alkyl or aryl sulfonic acids represented by dioctyl sulfosuccinic acid and dodecylbenzenesulfonic acid, or alkyl or aryl ether sulfonic acids, (a2) alkyl or aryl sulfuric acids represented by dodecyl sulfuric acid, or alkyl or aryl ether sulfuric acids, (a3) alkyl or aryl-substituted phosphoric acids, or alkyl or aryl ether-substituted phosphoric acids, (a4) N-alkyl or aryl sarcosines represented by dodecyl sarcosine, (a5) alkyl or aryl carboxylic acids represented by oleic acid and stearic acid, or alkyl or aryl ether carboxylic acids, etc. Here, the anionic emulsifiers formed from the acids described in the above (a1) and (a2) are called sulfur-based emulsifiers, the anionic emulsifiers formed from the acids described in the above (a3) are called phosphorus-based emulsifiers, the anionic emulsifiers formed from the acids described in the above (a4) are called sarcosine-based emulsifiers, and the anionic emulsifiers formed from the acids described in the above (a5) are called carboxylic acid-based emulsifiers. These emulsifiers can be used alone or in combination of two or more.

[0204] As a method for producing the polymer particles (A), in the case of using emulsion polymerization, a thermal decomposition initiator can be used in the production of the polymer particles (A). Examples of the above thermal decomposition initiator include known initiators such as 2,2'-azobisisobutyronitrile, hydrogen peroxide, potassium persulfate, and ammonium persulfate.

[0205] A redox initiator can also be used in the production of the polymer particles (A). The above-mentioned redox initiator is an initiator that combines the following (a) and (b): (a) peroxides such as organic peroxides and inorganic peroxides; (b) reducing agents such as sodium formaldehyde sulfoxylate and glucose added as needed, transition metal salts such as iron(II) sulfate added as needed, chelating agents such as disodium ethylenediaminetetraacetate added as needed, and phosphorus-containing compounds such as sodium pyrophosphate added as needed. Examples of the above-mentioned organic peroxides include: tert-butyl peroxyisopropyl carbonate, p-menthane hydroperoxide, cumene hydroperoxide, dicumyl peroxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, and tert-hexyl peroxide. Examples of the above-mentioned inorganic peroxides include: hydrogen peroxide, potassium persulfate, ammonium persulfate, etc.

[0206] When using a redox initiator, polymerization can be carried out at a low temperature where the above-mentioned peroxides do not substantially undergo thermal decomposition, and the polymerization temperature can be set within a wide range. Therefore, it is preferable to use a redox initiator. Among the redox initiators, it is preferable to use organic peroxides such as cumene hydroperoxide, dicumyl peroxide, p-menthane hydroperoxide, and tert-butyl hydroperoxide as the redox initiator. The dosage of the above-mentioned initiator, and the dosages of the above-mentioned reducing agent, transition metal salt, chelating agent, etc. when using a redox initiator can be used within a known range.

[0207] When a polyfunctional monomer is used in the polymerization of an elastomer, a graft portion, or a surface-crosslinked polymer in order to introduce a crosslinked structure into the elastomer, the graft portion, or the surface-crosslinked polymer, a known chain transfer agent can be used within a known dosage range. By using a chain transfer agent, the molecular weight and / or crosslinking degree of the obtained elastomer, graft portion, or surface-crosslinked polymer can be easily adjusted.

[0208] In the production of the polymer particles (A), in addition to the above-mentioned components, a surfactant can also be used. The type and dosage of the above-mentioned surfactant are within a known range.

[0209] In the production of the polymer particles (A), conditions such as the polymerization temperature, pressure, and deoxidation during polymerization can be applied within a known range.

[0210] (2-11. Resin (B))

[0211] As described above, in the present manufacturing method, resin (B) can be used, and the resulting powder particles can further contain resin (B). As resin (B), it can be the same type of resin as the matrix resin (C) that can be mixed with the powder particles, or it can be a different type of resin from the matrix resin (C). As an example, the case can be considered where resin (B) is used in the present manufacturing method, and the resulting powder particles are mixed with the matrix resin (C) of the same type as resin (B) to obtain a resin composition. In this case, in the resulting resin composition, resin (B) and the matrix resin (C) cannot be distinguished. Therefore, in appearance, the resulting resin composition seems to contain only the matrix resin (C) in addition to the polymer particles (A). Next, consider the case where resin (B) is used in the manufacturing method of the resin composition, and the resulting powder particles are mixed with a matrix resin (C) of a different type from resin (B) to obtain a resin composition. In this case, in the resulting resin composition, resin (B) and the matrix resin (C) can be distinguished. In this case, the finally obtained resin composition can contain resin (B) as a resin other than the matrix resin (C) in addition to the polymer particles (A).

[0212] Resin (B) can be, for example, a thermosetting resin, a thermoplastic resin, or any combination of a thermosetting resin and a thermoplastic resin. When the present powder particles contain resin (B), resin (B) can have the effect of improving the dispersibility of the polymer particles (A) in the resin composition containing the resulting powder particles.

[0213] As the thermosetting resin in resin (B), various thermosetting resins described in the item of the matrix resin (C) to be described later can be cited. In resin (B), only one type of thermosetting resin can be used, or two or more types can be used in combination.

[0214] As the thermoplastic resin in resin (B), various thermoplastic resins described in the item of the matrix resin (C) to be described later can be cited. In resin (B), only one type of thermoplastic resin can be used, or two or more types can be used in combination.

[0215] From the viewpoint of not worrying about affecting various physical properties of the resin composition, cured product, or molded article containing the resulting powder particles, it is preferable that resin (B) and the matrix resin (C) are of the same type. That is, when the matrix resin (C) is an epoxy resin, it is preferable that resin (B) is also an epoxy resin. When resin (B) and the matrix resin (C) are of different types, it is preferable that resin (B) and the matrix resin (C) are compatible.

[0216] (Physical properties of resin (B))

[0217] The properties of resin (B) are not particularly limited. Resin (B) is preferably a liquid having a viscosity of 100 mPa·s to 1,000,000 mPa·s at 25°C, or a semi-solid, or a solid. It should be noted that "resin (B) has a viscosity of 100 mPa·s to 1,000,000 mPa·s at 25°C" means that "resin (B) at 25°C has a viscosity of 100 mPa·s to 1,000,000 mPa·s".

[0218] When resin (B) is a liquid, the viscosity of resin (B) at 25°C is preferably 750,000 mPa·s or less, more preferably 700,000 mPa·s or less, more preferably 500,000 mPa·s or less, more preferably 350,000 mPa·s or less, more preferably 300,000 mPa·s or less, more preferably 250,000 mPa·s or less, more preferably 100,000 mPa·s or less, more preferably 75,000 mPa·s or less, more preferably 50,000 mPa·s or less, more preferably 30,000 mPa·s or less, more preferably 25,000 mPa·s or less, further preferably 20,000 mPa·s or less, and particularly preferably 15,000 mPa·s or less. With the above configuration, resin (B) has the advantage of excellent fluidity. Resin (B) having a viscosity of 100 mPa·s to 1,000,000 mPa·s at 25°C can be considered a liquid.

[0219] In addition, from the viewpoint of preventing the polymer particles (A) in the powder and the resin composition from sticking to each other by allowing resin (B) to enter the polymer particles (A), the viscosity of resin (B) at 25°C is 200 mPa·s or more, more preferably 300 mPa·s or more, more preferably 400 mPa·s or more, more preferably 500 mPa·s or more, further preferably 750 mPa·s or more, still more preferably 1000 mPa·s or more, and particularly preferably 1500 mPa·s or more.

[0220] The viscosity of resin (B) at 25°C is more preferably 100 mPa·s to 750,000 mPa·s, more preferably 100 mPa·s to 700,000 mPa·s, more preferably 100 mPa·s to 350,000 mPa·s, more preferably 100 mPa·s to 300,000 mPa·s, more preferably 100 mPa·s to 50,000 mPa·s, further preferably 100 mPa·s to 30,000 mPa·s, and particularly preferably 100 mPa·s to 15,000 mPa·s.

[0221] Resin (B) may have a viscosity greater than 1,000,000 mPa·s. Resin (B) may be semi-solid (semi-liquid) or solid. When resin (B) has a viscosity greater than 1,000,000 mPa·s, the resulting resin composition containing the powder particles has the advantages of less stickiness and easy handling.

[0222] In addition, the viscosity of resin (B) at 25°C is preferably not more than the value obtained by adding 50,000 mPa·s to the viscosity of matrix resin (C) at 25°C. From the viewpoint of easily mixing resin (B) and matrix resin (C) uniformly, when the viscosity of resin (B) at 25°C is not less than the viscosity of matrix resin (C) at 25°C, the viscosity of resin (B) at 25°C is more preferably not more than the value obtained by adding 20,000 mPa·s to the viscosity of matrix resin (C) at 25°C, still more preferably not more than the value obtained by adding 10,000 mPa·s, further preferably not more than the value obtained by adding 5,000 mPa·s, and most preferably not more than the value obtained by adding 0 mPa·s.

[0223] The viscosity of resin (B) can be measured by a viscometer. The measuring method of the viscosity of resin (B) is described in detail in the following examples.

[0224] In addition, resin (B) is preferably a resin whose differential scanning calorimetry (DSC) thermogram has an endothermic peak at 25°C or lower, and more preferably a resin having an endothermic peak at 0°C or lower.

[0225] When resin (B) is used in this production method, regarding the mixing ratio of polymer particles (A) and resin (B), when the total of polymer particles (A) and resin (B) is set to 100% by weight, polymer particles (A) are preferably 50 to 99% by weight and resin (B) is 1 to 50% by weight. In addition, from the viewpoint of anti-blocking property, polymer particles (A) are more preferably 70 to 99% by weight and resin (B) is 1 to 30% by weight, still more preferably polymer particles (A) are 80 to 99% by weight and resin (B) is 1 to 20% by weight, particularly preferably polymer particles (A) are 90 to 99% by weight and resin (B) is 1 to 10% by weight, and most preferably polymer particles (A) are 95 to 99% by weight and resin (B) is 1 to 5% by weight.

[0226] In addition, from the viewpoint of the dispersibility of the polymer particles (A) in the matrix resin (C) (hereinafter also simply referred to as "dispersibility"), with respect to the mixing ratio of the polymer particles (A) and the resin (B), when the total of the polymer particles (A) and the resin (B) is 100% by weight, the polymer particles (A) are preferably 60 to 95% by weight and the resin (B) is 5 to 40% by weight, more preferably the polymer particles (A) are 60 to 90% by weight and the resin (B) is 10 to 40% by weight, still more preferably the polymer particles (A) are 60 to 85% by weight and the resin (B) is 15 to 40% by weight, and most preferably the polymer particles (A) are 60 to 80% by weight and the resin (B) is 20 to 40% by weight.

[0227] In the transmission electron microscope (TEM) image of the obtained powder particles, from the viewpoint of preventing the polymer particles (A) from sticking to each other, the number of microregions where the major axis of the resin (B) is 1.5 times or more the average particle diameter of the polymer particles (A) is preferably 5 or less, more preferably 3 or less, still more preferably 1 or less, and most preferably 0 or less. That the number of microregions where the major axis of the resin (B) is 1.5 times or more the average particle diameter of the polymer particles (A) is 0 or less in the transmission electron microscope (TEM) image means that there is no microregion where the major axis of the resin (B) is 1.5 times or more the average particle diameter of the polymer particles (A) in the transmission electron microscope (TEM) image.

[0228] The major axis of the resin (B) refers to the maximum length in the TEM image (the length of the longest straight line among the straight lines connecting two points on the outer periphery). In addition, the average particle diameter of the polymer particles (A) refers to, for example, in the TEM image, the average value of the diameters (area equivalent circle diameters) of circles having the same area as the projected areas of 30 randomly selected polymer particles (A) each.

[0229] (Other components of the resin (B))

[0230] In this specification, oils and fats and fatty acid esters are also included in the resin (B). Examples of oils and fats that can be suitably used as the resin (B) include: epoxidized oils such as epoxidized soybean oil and epoxidized linseed oil. As epoxidized soybean oil, commercially available products can be used, and examples include: ADEKAIZER O-130P manufactured by ADEKA Corporation. Examples of fatty acid esters that can be suitably used as the resin (B) include: epoxidized fatty acid butyl esters, epoxidized fatty acid 2-ethylhexyl esters, epoxidized fatty acid octyl esters, and epoxidized fatty acid alkyl esters.

[0231] Epoxidized oils and epoxidized fatty acid esters are sometimes also referred to as epoxy plasticizers. That is, in this specification, epoxy plasticizers are also included in resin (B). As epoxy plasticizers other than epoxidized oils and epoxidized fatty acid esters, examples include: diepoxystearyl epoxidized hexahydrophthalate, bis(2-ethylhexyl) epoxidized hexahydrophthalate, and the like.

[0232] The above-mentioned thermosetting resin, thermoplastic resin, mixture of thermosetting resin and thermoplastic resin, oil, and fatty acid ester can each be used in admixture with an antioxidant. In this specification, when used in admixture with each of the above substances, the antioxidant is regarded as a part of resin (B). When only the antioxidant is used, the antioxidant is not regarded as resin (B).

[0233] The antioxidant is not particularly limited. Examples of the antioxidant include: (a) first antioxidants such as phenolic antioxidants, amine antioxidants, lactone antioxidants, and hydroxylamine antioxidants, and (b) second antioxidants such as sulfur antioxidants and phosphorus antioxidants.

[0234] As the above-mentioned phenolic antioxidant, a hindered phenolic antioxidant can be cited. As the hindered phenolic antioxidant, a compound having a hindered phenol structure or a semi-hindered phenol structure in the molecule can be cited. As the phenolic antioxidant, commercially available products can also be used, and examples include IRGANOX 245 manufactured by BASF JAPAN Co., Ltd.

[0235] As the above-mentioned amine antioxidant, there is no particular limitation, and known amine antioxidants can be widely used. Specific examples of the amine antioxidant include 2,2,4-trimethyl-1,2-dihydroquinoline polymer, 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline, and reaction products of diphenylamine and acetone, which are amine-ketone compounds.

[0236] The above-mentioned amine antioxidant may also include aromatic amine compounds. Examples of the aromatic amine compounds include: naphthylamine antioxidants, diphenylamine antioxidants, and p-phenylenediamine antioxidants.

[0237] As the lactone antioxidant, hydroxylamine antioxidant, and sulfur antioxidant, there is no particular limitation, and known antioxidants can be widely used.

[0238] As the phosphorus-based antioxidant, there is no particular limitation, and conventionally well-known phosphorus-based antioxidants can be widely used. Phosphoric acid and phosphate esters containing active hydrogen have an adverse effect on the storage stability of the resin composition containing the obtained powder particles and the heat resistance of the cured product or molded article provided by the resin composition. Therefore, as the phosphorus-based antioxidant, preferably used are alkyl phosphite, aryl phosphite, alkylaryl phosphite compounds, etc. that do not contain phosphoric acid and phosphate esters in the molecule.

[0239] As the above antioxidant, other than that, conventionally well-known substances can also be used. As the antioxidant, various substances described in, for example, "Antioxidant Handbook" published by Dainippon Ink and Chemicals, Incorporated (first edition released on October 25, 1976), "Polymer Additive Handbook" published by CMC Publishing Co., Ltd. (edited by Toru Haruna, first edition released on November 7, 2010), etc. can be used.

[0240] The resin (B) is preferably at least one selected from the group consisting of a thermosetting resin, a mixture of a thermosetting resin and an antioxidant, a thermoplastic resin, a mixture of a thermoplastic resin and an antioxidant, an oil, a mixture of an oil and an antioxidant, a fatty acid ester, a mixture of a fatty acid ester and an antioxidant, an epoxy curing agent, and a mixture of an epoxy curing agent and an antioxidant, more preferably at least one selected from the group consisting of an epoxy resin, an acrylic polymer, a mixture of an epoxy resin and an antioxidant, a mixture of an acrylic polymer and an antioxidant, and a mixture of an epoxy plasticizer and an antioxidant, further preferably at least one 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 plasticizer and an antioxidant, and particularly preferably a mixture of an epoxy plasticizer and an antioxidant. With this configuration, the following advantages are achieved: (a) the resin composition containing the obtained powder particles can provide a cured product or molded article having excellent heat resistance, and (b) the dispersibility of the polymer fine particles (A) in the matrix resin is improved.

[0241] (2-12. Anti-blocking agent)

[0242] In this manufacturing method, from the viewpoint of improving anti-blocking properties and dispersibility in the matrix resin (C), it is preferable to further use an anti-blocking agent. In other words, the powder particles obtained by this manufacturing method preferably further contain an anti-blocking agent. The anti-blocking agent only needs to exhibit the above-mentioned effects and is not particularly limited. Examples of the anti-blocking agent include: (i) an anti-blocking agent containing inorganic fine particles such as silica, titanium oxide, alumina, zirconia, aluminum silicate, diatomaceous earth, zeolite, kaolin, talc, calcium carbonate, calcium phosphate, barium sulfate, and magnesium hydrosilicate; (ii) an anti-blocking agent containing organic fine particles; (iii) waxes such as polyethylene wax, higher fatty acid amides, metal soaps, and silicone oils. Among them, as the anti-blocking agent, an anti-blocking agent containing fine particles (inorganic fine particles or organic fine particles) is preferred, and an anti-blocking agent containing organic fine particles is more preferred. As the anti-blocking agent, an anti-blocking agent containing organic fine particles of a polymer is particularly preferred, and the polymer contains a structural unit derived from one or more monomers selected from aromatic vinyl monomers, vinyl cyanide monomers, and (meth)acrylate monomers as a structural unit.

[0243] The anti-blocking agent containing fine particles is usually formed by dispersing fine particles in a liquid or is colloidal. The volume average particle diameter (Mv) of the fine particles in the anti-blocking agent is usually 10 μm or less, preferably 0.05 to 10 μm. The content of the anti-blocking agent 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 powder particles.

[0244] The anti-blocking agent and any other components described below can be appropriately added in any step of this manufacturing method. For example, the anti-blocking agent and any other components can be added to the latex before the spraying step, or can be added by directly mixing with the obtained powder particles.

[0245] (2-13. Powder particles)

[0246] In this manufacturing method, aggregates containing polymer particles (A), that is, powder particles, can be obtained. For the powder particles obtained by this manufacturing method, the water content based on the weight of the powder particles is preferably 50% or more, more preferably 55% or more, further preferably 60% or more, and particularly preferably 65% or more. In this manufacturing method, since it is not necessary to dry the powder particles obtained in the spraying step, powder particles with a water content of 50% or more can be easily obtained. The powder particles with a water content of 50% or more have the following advantages: (a) excellent dispersibility of the polymer particles (A) in the resin composition when the matrix resin (C) described below is mixed with the powder particles to form a resin composition; (b) less generation of fine powder; (c) excellent moldability.

[0247] The powdery particles obtained by this manufacturing method preferably have few inclusions. In this manufacturing method, since powdery particles can be obtained without using an electrolyte, powdery particles with few inclusions can be obtained.

[0248] Inclusions, also known as impurities, refer to compounds such as inorganic salts and organic salts, and components derived from emulsifiers. Examples of inclusions include calcium element and chlorine element. The inclusions in the powdery particles can be detected and quantified using a fluorescent X-ray analyzer, ion chromatography, gas chromatography, etc.

[0249] [3. Method for manufacturing particles]

[0250] The method for manufacturing particles according to one embodiment of the present invention has a step of molding the powdery particles manufactured by the method for manufacturing powdery particles described in [2. Method for manufacturing powdery particles] into a granular shape. The powdery particles obtained by this manufacturing method have a high water content, so they can be easily molded into a granular shape, that is, they have excellent moldability. Specifically, when molding the powdery particles obtained by the prior art into a granular shape, melt extrusion molding in which the powdery particles are heated and molded is required. However, the powdery particles obtained by this manufacturing method can be molded into a granular shape by a molding method called extrusion granulation without heating. Therefore, the powdery particles obtained by this manufacturing method can provide particles with excellent quality such as hue without using a heat stabilizer. It should be noted that the particles according to one embodiment of the present invention can also be manufactured by melt extrusion molding using the powdery particles. In one embodiment of the present invention, molding can be performed without heating. Therefore, compared with melt extrusion molding, it is preferable to manufacture the particles by the molding method of extrusion granulation. Particles are also called pellets. The terms "particles" and "pellets" can be used interchangeably.

[0251] The method for manufacturing particles according to one embodiment of the present invention can provide particulate polymer microparticles (A) in the form of particles, specifically, powdery particles in a granular shape. Compared with powdery particles, particles have the advantages of being easy to operate, being easily mixed with a granular matrix resin (not easily classified), and not easily adhering to the body and devices, etc.

[0252] The particles according to one embodiment of the present invention can be (a) particles containing the powdery particles according to one embodiment of the present invention obtained by aggregating the polymer microparticles (A) according to one embodiment of the present invention. Additionally, they can also be (b) a molded product of the powdery particles obtained by molding the powdery particles according to one embodiment of the present invention obtained by aggregating the polymer microparticles (A) according to one embodiment of the present invention.

[0253] In this specification, a particle refers to a substance where, when the substance is passed through a sieve with a mesh size of 4 mm, the value obtained by dividing the weight of the above-mentioned polymer fine particles (A) passing through the sieve by the weight of the substance before sieving and multiplying the resulting value by 100 is 5% or less. Here, for the method of sieving the substance containing the polymer fine particles (A), the description of the sieving method in the following (5-2. Disintegration rate) can be cited.

[0254] In the step of forming into particles, the method of forming the powder into particles is not particularly limited, and examples thereof that can be preferably cited include: a method using a kneader or an extruder, a method using a tablet press, and a method using a rolling granulator.

[0255] The particles manufactured by the method for manufacturing particles according to one embodiment of the present invention are also included in one embodiment of the present invention. The particles according to one embodiment of the present invention are granular powder, and can also be said to be granular polymer fine particles (A).

[0256] The disintegration rate of the particles according to one embodiment of the present invention is preferably 5% or less. Here, the above-mentioned disintegration rate refers to the value obtained by dividing the weight of the above-mentioned polymer fine particles (A) passing through the sieve by the weight of the above-mentioned particles before sieving when the particles are passed through a sieve with a mesh size of 4 mm and multiplying the resulting value by 100. For the sieving method when evaluating the disintegration rate of the particles, the description of the sieving method in the following (5-2. Disintegration rate) is cited.

[0257] The disintegration rate of the particles according to one embodiment of the present invention is 5% or less, preferably 4% or less, more preferably 3% or less, and further preferably 2% or less. With this configuration, there is an advantage that less fine powder is generated.

[0258] The particles according to one embodiment of the present invention can have the following configuration. That is, the particles according to one embodiment of the present invention are particles containing a powder obtained by aggregating polymer fine particles, the above-mentioned polymer fine particles (a) contain a graft copolymer having a graft portion, and (b) have a volume average particle size of 0.03 μm to 2.00 μm and a disintegration rate of 5% or less. Here, the above-mentioned disintegration rate refers to the value obtained by dividing the weight of the above-mentioned powder passing through the sieve by the weight of the above-mentioned particles before sieving when the particles are passed through a sieve with a mesh size of 4 mm and multiplying the resulting value by 100.

[0259] The particles according to one embodiment of the present invention can further contain a resin (B). For the resin (B), the description in item (2-11. Resin (B)) can be appropriately cited.

[0260] The particles according to one embodiment of the present invention can contain components other than the powder according to one embodiment of the present invention (for example, resin (B), an anti-adhesion agent, and other optional components described in item (6-5. Other optional components)).

[0261] Particles according to an embodiment of the present invention preferably contain 70% by weight or more, more preferably 75% by weight or more, still more preferably 80% by weight or more, still more preferably 85% by weight or more, further preferably 90% by weight or more, and particularly preferably 95% by weight or more of the powder particles according to an embodiment of the present invention in 100% by weight of the particles.

[0262] 〔4. Method for manufacturing dry powder〕

[0263] The method for manufacturing a dry powder according to an embodiment of the present invention has a step of drying the powder particles produced by the method for manufacturing powder particles described in item 〔2. Method for manufacturing powder particles〕. By drying the powder particles to produce a dry powder, there are advantages of easy operation and easy mixing with a powdery matrix resin (not easily classified).

[0264] In the step of drying, the method for drying the powder particles is not particularly limited, and examples thereof may preferably include: a method using a dryer, and a method of spraying a heated gas onto the powder particles.

[0265] When drying the powder particles using a dryer, the temperature inside the dryer and the time for placing the powder particles in the dryer are not particularly limited. In addition, when spraying a heated gas onto the powder particles, the temperature of the heated gas is not particularly limited.

[0266] 〔5. Powder particles〕

[0267] The powder particles according to an embodiment of the present invention are powder particles formed by aggregating polymer fine particles, and the polymer fine particles (a) contain a graft copolymer having a graft portion, and (b) have a volume average particle diameter of 0.03 μm to 2.00 μm and a disintegration rate of 5% or less. Here, the disintegration rate refers to a value obtained by dividing the weight of the powder particles passing through a sieve with a mesh size of 4 mm by the weight of the molded product before sieving after compacting the powder particles to form a molded product using a cylindrical roller with a diameter of 17 mm at a pressure of 100 kPa or more, and multiplying the obtained value by 100. Hereinafter, the powder particles according to an embodiment of the present invention may sometimes be simply referred to as the present powder particles. The present powder particles can also be said to be powder particles containing an aggregate of polymer fine particles (A).

[0268] Since the present powder particles have the above composition, they have the following advantages: (a) excellent dispersibility of the polymer fine particles (A) in the resin composition when mixing the matrix resin (C) described later and the powder particles to form a resin composition; (b) less generation of fine powder; (c) excellent moldability.

[0269] The aggregate may contain components other than the polymer fine particles (A) (for example, resin (B), an anti-blocking agent, and any other components described in item (6-5. Any other components)). The powder particles obtained by this production method may contain components other than the aggregate containing the polymer fine particles (A) (for example, resin (B), an anti-blocking agent, and any other components described in item (6-5. Any other components)).

[0270] The powder particles obtained by this production method preferably contain 35% by weight or more of the polymer fine particles (A), more preferably 40% by weight or more, still more preferably 45% by weight or more, and particularly preferably 50% by weight or more based on 100% by weight of the powder particles.

[0271] This powder particles is preferably produced by the production method described in item [2. Production method of powder particles]. When this powder particles is produced by the production method described in item [2. Production method of powder particles], it has the advantages of less inclusions (impurities), less environmental burden, and higher moisture content.

[0272] Hereinafter, specific embodiments related to this powder particles will be described. Except for the matters described in detail below, the description of [2. Production method of powder particles] will be appropriately cited.

[0273] (5-1. Volume average particle diameter)

[0274] From the viewpoint that the resin composition containing the obtained powder particles has a desired viscosity and is highly stable, the volume average particle diameter (Mv) of the polymer fine particles (A) is preferably 0.03 μm to 2 μm, more preferably 0.05 to 1 μm, and still more preferably 0.1 to 0.8 μm. From the viewpoint that the dispersibility of the polymer fine particles (A) in the thermosetting resin or thermoplastic resin becomes good, the volume average particle diameter (Mv) of the polymer fine particles (A) is further preferably 0.1 to 0.5 μm. For the measurement method and other aspects of the volume average particle diameter of the polymer fine particles (A), the description of the item (Volume average particle diameter (Mv) of the polymer fine particles (A)) in (2-9. Polymer fine particles (A)) can be appropriately cited.

[0275] (5-2. Disintegration rate)

[0276] The disintegration rate of this powder particles is 5% or less, preferably 4% or less, more preferably 3% or less, and still more preferably 2% or less. With this configuration, it has the advantages of less generation of fine powder and excellent moldability.

[0277] When evaluating the disintegration rate, the method for producing the molded article is not particularly limited. For example, a method can be cited in which 1 g of powder particles are put into a plastic cylindrical drum with an inner diameter of 13 mm and a height of 17 mm, and then a load of 104 kPa is applied to the powder particles in the drum for 30 seconds using a plunger.

[0278] The method for sieving when evaluating the disintegration rate is not particularly limited, and a known method can be used. For example, a method can be cited in which the molded article of powder particles is placed on a sieve with a mesh size of 4 mm, and then the two sides of the sieve are grasped with both hands and moved horizontally to the left and right. As the mode of movement, for example, with an amplitude of about 75 mm and one round trip as one time (that is, the moving distance for each time is about 150 mm (= about 75 mm × 2)), it is vibrated at a speed of 20 times / 10 seconds for 20 seconds.

[0279] (5-3. Resin (B))

[0280] This powder particle may further contain resin (B). For resin (B), the description in item (2-11. Resin (B)) can be appropriately cited.

[0281] (5-4. Moisture content)

[0282] Based on the weight of the powder particles, the moisture content of this powder particle is preferably 50% or more, more preferably 55% or more, further preferably 60% or more, and particularly preferably 65% or more. With this configuration, there are the following advantages: (a) when the matrix resin (C) described later is mixed with the powder particles to form a resin composition, the dispersibility of the polymer particles (A) in the resin composition is excellent, (b) less fine powder is generated, and (c) it is easy to form granules.

[0283] (5-5. Dispersibility)

[0284] Regarding this powder particle, when preparing a dispersion aqueous solution by dispersing the powder particle in water, it is preferred that in this dispersion aqueous solution, 90% by volume or more of the above polymer particles contained in the powder particle are dispersed in the form of primary particles. With this configuration, there is an advantage that when the matrix resin (C) described later is mixed with the powder particles to form a resin composition, the dispersibility of the polymer particles (A) in the resin composition is excellent.

[0285] As the method for dispersing the powder particle in water, it is not particularly limited, and for example, a method of stirring using a stirrer can be cited. As the stirring conditions, it is not particularly limited, and conditions such as stirring at 300 rpm to 500 rpm for 30 seconds to 1 minute can be cited.

[0286] In a dispersion aqueous solution, polymer fine particles (A) dispersed in the form of primary particles and polymer fine particles (A) dispersed in the form of secondary particles formed by coagulation of several primary particles of the polymer fine particles (A) can exist. As a method for calculating the proportion of the polymer fine particles (A) contained in the powder particles in the dispersion aqueous solution that are dispersed in the form of primary particles, there can be mentioned a method of measuring the volume average particle diameter of the polymer fine particles (A) dispersed in the dispersion aqueous solution (which may include primary particles and secondary particles), dividing the obtained value by the volume average particle diameter of the primary particles of the polymer fine particles (A), and multiplying the obtained value by 100. The volume average particle diameter of the polymer fine particles (A) (which may include primary particles and secondary particles) dispersed in the dispersion aqueous solution can be measured using a laser diffraction particle size distribution analyzer (LA-950 manufactured by Horiba, Ltd.) or a dynamic light scattering particle size distribution analyzer (Zetasizer ZSP manufactured by Malvern) with the dispersion aqueous solution as a sample. As described above, the volume average particle diameter of the primary particles of the polymer fine particles (A) can be measured using a dynamic light scattering particle size distribution measuring device or the like with an aqueous latex containing the polymer fine particles (A) as a sample.

[0287] [6. Resin Composition]

[0288] A resin composition containing a matrix resin and powder particles obtained by the production method described in item [2. Production Method of Powder Particles], particles obtained by the production method described in item [3. Production Method of Granules], dry powder obtained by the production method described in item [4. Production Method of Dry Powder], or powder particles described in item [5. Powder Particles] is also an embodiment of the present invention. Hereinafter, the resin composition of an embodiment of the present invention may sometimes be simply referred to as this resin composition. The matrix resin contained in this resin composition is also referred to as "matrix resin (C)".

[0289] (6-1. Matrix Resin (C))

[0290] As the matrix resin (C), a thermosetting resin or a thermoplastic resin can be preferably used.

[0291] (6-1-1. Thermosetting Resin)

[0292] The thermosetting resin preferably contains at least one thermosetting resin selected from resins containing polymers formed by polymerizing ethylenically unsaturated monomers, epoxy resins, phenolic resins, polyol resins, and amino-formaldehyde resins. In addition, as the thermosetting resin, a resin containing a polymer formed by polymerizing aromatic polyester raw materials can also be cited. Examples of the aromatic polyester raw materials include free-radical polymerizable monomers such as aromatic vinyl compounds, (meth)acrylic acid derivatives, vinyl cyanide compounds, and maleimide compounds, dimethyl terephthalate, alkylene glycols, etc. These thermosetting resins can be used alone or in combination of two or more.

[0293] (ethylenically unsaturated monomer)

[0294] As the ethylenically unsaturated monomer, it is only necessary that it has at least one ethylenic unsaturated bond in the molecule, and there is no particular limitation.

[0295] Examples of the ethylenically unsaturated monomer include acrylic acid, α-alkylacrylic acid, α-alkylacrylate, β-alkylacrylic acid, β-alkylacrylate, methacrylic acid, esters of acrylic acid, esters of methacrylic acid, vinyl acetate, vinyl esters, unsaturated esters, polyunsaturated carboxylic acids, polyunsaturated esters, maleic acid, maleic acid esters, maleic anhydride, and acetoxystyrene. These can be used alone or in combination of two or more.

[0296] (epoxy resin)

[0297] As the epoxy resin, it is only necessary that it has at least one epoxy bond in the molecule, and there is no particular limitation.

[0298] As specific examples of the epoxy resin, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, novolak type epoxy resin, glycidyl ether type epoxy resin of bisphenol A propylene oxide adduct, hydrogenated bisphenol A (or F) type epoxy resin, fluorinated epoxy resin, rubber-modified epoxy resin containing polybutadiene or NBR, flame-retardant epoxy resin such as glycidyl ether of tetrabromobisphenol A, glycidyl ether ester type epoxy resin of p-hydroxybenzoic acid, m-aminophenol type epoxy resin, diaminodiphenylmethane type epoxy resin, urethane-modified epoxy resin having a urethane bond, various alicyclic epoxy resins, glycidyl ether of polyol, epoxy resin of hydantoin type, epoxy of unsaturated polymers such as petroleum resin, and amino-containing glycidyl ether resin, etc. As the above polyol, for example, N,N-diglycidylaniline, N,N-diglycidyl-o-toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether, and glycerol, etc. can be cited. As the epoxy resin, an epoxy compound obtained by adding bisphenol A (or F) type, polybasic acid type, etc. to the above epoxy resin can be cited. The epoxy resin is not limited thereto, and a commonly used epoxy resin can be used. These epoxy resins can be used alone or in combination of two or more kinds.

[0299] Among the above epoxy resins, from the viewpoints of high reactivity in the curing of the resin composition and the cured product being easily formed into a three-dimensional network, etc., a resin having at least 2 epoxy groups in one molecule is preferred. Further, as the epoxy resin, from the viewpoints of excellent economy and ease of obtaining, among the epoxy resins having at least 2 epoxy groups in one molecule, an epoxy resin mainly composed of bisphenol type epoxy resin is preferred.

[0300] (Phenolic resin)

[0301] The phenolic resin may be any compound obtained by reacting phenols with aldehydes, and is not particularly limited. As the phenols, there is no particular limitation, and for example, phenols such as phenol, o-cresol, m-cresol, p-cresol, xylenol, p-butylphenol, p-octylphenol, p-phenylphenol, bisphenol A, bisphenol F, and resorcinol can be cited. As particularly preferred phenols, phenol and cresol can be cited.

[0302] As the aldehydes, there is no particular limitation, and for example, formaldehyde, acetaldehyde, butyraldehyde, acrolein, etc., and mixtures thereof can be cited. As the aldehydes, a substance that is a source of the above aldehydes or a solution of these aldehydes can also be used. As the aldehydes, from the viewpoint of easy operation when reacting phenols with aldehydes, formaldehyde is preferred.

[0303] When reacting phenols with aldehydes, the molar ratio of aldehydes (F) to phenols (P) (hereinafter also referred to as the reaction molar ratio) is not particularly limited. When an acid catalyst is used in the reaction, the above reaction molar ratio (F / P) is preferably 0.4 to 1.0, more preferably 0.5 to 0.8. When a base catalyst is used in the reaction, the above reaction molar ratio (F / P) is preferably 0.4 to 4.0, more preferably 0.8 to 2.5. When the reaction molar ratio is at or above the lower limit value, the yield will not be overly reduced, and there is no risk of a decrease in the molecular weight of the resulting phenolic resin. On the other hand, when the reaction molar ratio is at or below the upper limit value, the molecular weight of the phenolic resin will not be too large and the softening point will not become too high, so sufficient fluidity can be obtained during heating. In addition, when the reaction molar ratio is at or below the upper limit value, the control of the molecular weight is easy, and there is no risk of gelation or the formation of local gel-like substances due to reaction conditions.

[0304] (Polyol resin)

[0305] The polyol resin is a compound having two or more active hydrogens at the ends and is a polyol having two or more functional groups with a molecular weight of about 50 to 20,000. Examples of the polyol resin include: aliphatic alcohols, aromatic alcohols, polyether polyols, polyester polyols, polyolefin polyols, and acrylic polyols.

[0306] The aliphatic alcohol can be any one of diols or alcohols with three or more hydroxyl groups (triols, tetrols, etc.). Examples of diols include: alkylene glycols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, etc. (especially alkylene glycols with about 1 to 6 carbon atoms), dehydration condensates of two or more molecules (e.g., about 2 to 6 molecules) of the above alkylene glycols (diethylene glycol, dipropylene glycol, tripropylene glycol, etc.). Examples of triols include: glycerol, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, etc. (especially triols with about 3 to 10 carbon atoms). Examples of tetrols include pentaerythritol, diglycerol, etc. In addition, saccharides such as monosaccharides, oligosaccharides, and polysaccharides can be listed.

[0307] Examples of aromatic alcohols include: bisphenols such as bisphenol A and bisphenol F; biphenyls such as dihydroxybiphenyl; polyphenols such as hydroquinone and phenol formaldehyde condensates; naphthalenediols, etc.

[0308] Examples of the polyether polyol include random copolymers or block copolymers obtained by ring-opening polymerization of ethylene oxide, propylene oxide, butylene oxide, styrene oxide, etc. in the presence of one or more active hydrogen-containing initiators, mixtures of these copolymers, and the like. Examples of the active hydrogen-containing initiator used in the ring-opening polymerization of the polyether polyol include diols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and bisphenol A; triols such as trimethylolethane, trimethylolpropane, and glycerol; saccharides such as monosaccharides, oligosaccharides, and polysaccharides; sorbitol; amines such as ammonia, ethylenediamine, urea, monomethyldiethanolamine, and monoethyldiethanolamine; and the like.

[0309] Examples of the polyester polyol include polymers obtained by polycondensing (a) polyacids such as maleic acid, fumaric acid, adipic acid, sebacic acid, phthalic acid, dodecanedioic acid, isophthalic acid, and azelaic acid and / or their acid anhydrides with (b) polyols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, and 3-methyl-1,5-pentanediol in the presence of an esterification catalyst at a temperature range of 150 to 270°C. In addition, examples of (a) the polyester polyol include ring-opening polymers of ε-caprolactone, valerolactone, etc., and (b) active hydrogen compounds having two or more active hydrogens such as polycarbonate diol and castor oil.

[0310] Examples of the polyolefin polyol include polybutadiene polyol, polyisoprene polyol, and their hydrides.

[0311] Examples of the acrylic polyol include copolymers of (a) hydroxyl group-containing monomers such as (meth)acrylic acid hydroxyethyl ester, (meth)acrylic acid hydroxybutyl ester, and vinylphenol and (b) general monomers such as n-butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate, and mixtures of these copolymers.

[0312] Among these polyol resins, polyether polyols are preferred from the viewpoints that the resin composition containing the obtained powder particles has low viscosity, excellent workability, and the resin composition can provide a cured product having an excellent balance between hardness and toughness. In addition, among these polyol resins, polyester polyols are preferred from the viewpoint that the resin composition containing the obtained powder particles can provide a cured product having excellent adhesiveness.

[0313] (Amino-formaldehyde resin)

[0314] The amino-formaldehyde resin is not particularly limited as long as it is a compound obtained by reacting an amino compound and an aldehyde in the presence of a basic catalyst. Examples of the above-mentioned amino compound include: melamine; 6-substituted guanamines such as guanamine, acetylguanamine, and benzoguanamine; amine-substituted triazine compounds such as CTU guanamine (3,9-bis[2-(3,5-diamino-2,4,6-triazinyl)ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane) and CMTU guanamine (3,9-bis[(3,5-diamino-2,4,6-triazinyl)methyl]-2,4,8,10-tetraoxaspiro[5,5]undecane); ureas such as urea, thiourea, and ethyleneurea. In addition, as the above-mentioned amino compound, a substituted melamine compound obtained by substituting the hydrogen of the amino group of melamine with an alkyl group, an alkenyl group, and / or a phenyl group (described in U.S. Patent No. 5,998,573 (corresponding Japanese Laid-Open Publication: Japanese Patent Laid-Open No. 9-143238)), and a substituted melamine compound obtained by substituting the hydrogen of the amino group of melamine with a hydroxyalkyl group, a hydroxyalkoxyalkyl group, and / or an aminoalkyl group (described in U.S. Patent No. 5,322,915 (corresponding Japanese Laid-Open Publication: Japanese Patent Laid-Open No. 5-202157)) can also be used. Among the above-mentioned amino compounds, from the viewpoints of industrial production and low cost, melamine, guanamine, acetylguanamine, and benzoguanamine as polyfunctional amino compounds are preferred, and melamine is particularly preferred. The above-mentioned amino compounds can be used alone or in combination of two or more. In addition to these amino compounds, (a) phenols such as phenol, cresol, alkylphenol, resorcinol, hydroquinone, and pyrogallol, and (b) aniline can be added.

[0315] Examples of the above-mentioned aldehydes include: formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, and furfural. Among the above-mentioned aldehydes, formaldehyde and paraformaldehyde are preferred from the viewpoints of low cost and good reactivity with the previously mentioned amino compounds. In the production of the amino-formaldehyde resin, it is preferred to use an aldehyde having an effective aldehyde group equivalent to 1.1 to 6.0 moles, and particularly preferably 1.2 to 4.0 moles, relative to 1 mole of the amino compound.

[0316] (6-1-2. Thermoplastic resin)

[0317] Specific examples of the thermoplastic resin include: acrylic polymers, vinyl copolymers, polycarbonates, polyamides, polyesters, polyphenylene ethers, polyurethanes, and polyvinyl acetates. These can be used alone or in combination of two or more.

[0318] The acrylic polymer has acrylate monomers as the main component. The number of carbon atoms in the ester moiety of the above acrylate monomers is preferably 1 to 20. In addition, examples of the acrylic polymer include: homopolymers of acrylate monomers, copolymers of acrylate monomers and monomers such as unsaturated fatty acids, acrylamide monomers, maleimide monomers, vinyl acetate, or vinyl copolymers. Examples of the acrylate monomer include, for example: methyl acrylate (MA), ethyl acrylate (EA), 2-ethylhexyl acrylate (2EHA), acrylic acid (AA), methacrylic acid (MA), 2-hydroxyethyl acrylate (2HEA), 2-hydroxyethyl methacrylate (2HEMA), butyl acrylate (BA), methyl methacrylate (MMA), ethyl methacrylate (EMA), n-butyl methacrylate (nBMA), isobutyl methacrylate (iBMA), methacrylic acid (MAA), propyl acrylate, isopropyl acrylate, isobutyl acrylate, tert-butyl acrylate, neopentyl acrylate, isodecyl acrylate, lauryl acrylate, tridecyl acrylate, stearyl acrylate, cyclohexyl acrylate, isobornyl acrylate, tricyclodecenyl acrylate, hydroxyethyl acrylate, hydroxybutyl acrylate, hydroxypropyl acrylate, hydroxyethyl acrylate, 2-methoxyethyl acrylate, dimethylaminoethyl acrylate, chloroethyl acrylate, trifluoroethyl acrylate, tetrahydrofurfuryl acrylate, etc. These can be used alone or in combination of two or more.

[0319] In the base resin (C), for the ratio of the acrylate monomer to the vinyl copolymer, unsaturated fatty acid, acrylamide monomer, maleimide monomer, and vinyl acetate, it is preferred that the acrylate monomer is 50% by weight to 100% by weight, and the acrylate monomer is 50% by weight to 100% by weight.

[0320] The acrylic polymer preferably contains 50% by weight or more of butyl acrylate (BA), more preferably 60% by weight or more, further preferably 70% by weight or more, particularly preferably 80% by weight or more, and most preferably 90% by weight or more.

[0321] The vinyl copolymer can be obtained by copolymerizing a mixture containing one or more monomers selected from aromatic vinyl monomers, vinyl cyanide monomers, and unsaturated carboxylic acid alkyl ester monomers. The mixture can further contain other monomers capable of copolymerizing with the above monomers.

[0322] Examples of the above aromatic vinyl monomers include, for example: styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, tert-butylstyrene, vinyltoluene, etc. These can be used alone or in combination of two or more. Among them, from the viewpoint of being able to easily increase the refractive index, styrene is preferred.

[0323] There is no particular limitation on the above-mentioned alkyl unsaturated carboxylate monomers. For example, esters formed from alcohols having 1 to 6 carbon atoms and acrylic acid or methacrylic acid are preferred. The esters formed from alcohols having 1 to 6 carbon atoms and acrylic acid or methacrylic acid may further have substituents such as a hydroxyl group or a halogen group.

[0324] Examples of the esters formed from alcohols having 1 to 6 carbon atoms and acrylic acid or methacrylic acid include: methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, chloromethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2,3,4,5,6-pentahydroxyhexyl (meth)acrylate, 2,3,4,5-tetrahydroxypentyl (meth)acrylate, etc. These may be used alone or in combination of two or more.

[0325] Examples of the vinyl cyanide monomers include: acrylonitrile, methacrylonitrile, ethylacrylonitrile, etc. These may be used alone or in combination of two or more.

[0326] As other monomers that can copolymerize with vinyl monomers, aromatic vinyl monomers, vinyl cyanide monomers, and alkyl unsaturated carboxylate monomers, as long as the effects of the present invention are not impaired, there is no particular limitation, and examples include: unsaturated fatty acids, acrylamide monomers, maleimide monomers, vinyl acetate, acrylate monomers, etc. These may be used alone or in combination of two or more.

[0327] Examples of the unsaturated fatty acids include: itaconic acid, maleic acid, fumaric acid, crotonic acid, acrylic acid, methacrylic acid, etc.

[0328] Examples of the acrylamide monomers include: acrylamide, methacrylamide, N-methylmethacrylamide, etc.

[0329] Examples of the maleimide monomers include: N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-dodecylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, etc.

[0330] There is no particular limitation on the method for producing the vinyl copolymer, and examples include: emulsion polymerization method, suspension polymerization method, bulk polymerization method, solution polymerization method, etc.

[0331] In the production of vinyl copolymers, a polymerization initiator can be used as needed. As the polymerization initiator, for example, one or more of peroxides, azo compounds, potassium persulfate, etc. can be appropriately selected.

[0332] Examples of peroxides include, for example: benzoyl peroxide, cumene hydroperoxide, diisopropylbenzene peroxide, diisopropylbenzene hydroperoxide, tert-butyl hydroperoxide, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, tert-butyl isopropyl carbonate, di-tert-butyl peroxide, tert-butyl peroxyoctanoate, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, and tert-butyl peroxy-2-ethylhexanoate, etc. Among them, cumene hydroperoxide, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, and 1,1-bis(tert-butylperoxy)cyclohexane are particularly preferably used.

[0333] Examples of azo compounds include, for example: azobisisobutyronitrile, azobis(2,4-dimethylvaleronitrile), 2-phenylazo-2,4-dimethyl-4-methoxypentanenitrile, 2-cyano-2-propyl azoformamide, 1,1'-azobiscyclohexane-1-carbonitrile, azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobisisobutyric acid dimethyl ester, 1-tert-butylazo-2-cyanobutane, and 2-tert-butylazo-2-cyano-4-methoxy-4-methylpentane, etc. Among them, 1,1'-azobiscyclohexane-1-carbonitrile is particularly preferably used.

[0334] In the production of vinyl copolymers, the addition amount of the above polymerization initiator is not particularly limited.

[0335] Specific examples of vinyl copolymers include: polyvinyl chloride, chlorinated polyvinyl chloride, polystyrene, styrene-acrylonitrile copolymer, styrene-acrylonitrile-N-phenylmaleimide copolymer, α-methylstyrene-acrylonitrile copolymer, polymethyl methacrylate, methyl methacrylate-styrene copolymer, etc. These can be used alone or in combination of two or more.

[0336] Examples of polyesters include polyethylene terephthalate and polybutylene terephthalate, etc.

[0337] (6-2. Physical properties of matrix resin (C))

[0338] The properties of the base resin (C) are not particularly limited. The base resin (C) preferably has a viscosity of 100 mPa·s to 1,000,000 mPa·s at 25°C. The viscosity of the base resin (C) is more preferably 50,000 mPa·s or less at 25°C, further preferably 30,000 mPa·s or less, and particularly preferably 15,000 mPa·s or less. With the above configuration, the base resin (C) has the advantage of excellent fluidity. The base resin (C) having a viscosity of 100 mPa·s to 1,000,000 mPa·s at 25°C can be considered a liquid.

[0339] The greater the fluidity of the base resin (C), in other words, the smaller the viscosity, the more difficult it is to disperse the polymer fine particles (A) in the state of primary particles in the base resin (C). Currently, it is very difficult to disperse the polymer fine particles (A) in the state of primary particles in the base resin (C) having a viscosity of 1,000,000 mPa·s or less at 25°C. However, the resin composition of one embodiment of the present invention has the advantage that the polymer fine particles (A) having the above configuration are well dispersed in the base resin (C) having a viscosity of 1,000,000 mPa·s or less at 25°C.

[0340] In addition, from the viewpoint of preventing the polymer fine particles (A) from sticking to each other by the base resin (C) entering the polymer fine particles (A), the viscosity of the base resin (C) is more preferably 100 mPa·s or more, further preferably 500 mPa·s or more, still further preferably 1000 mPa·s or more, and particularly preferably 1500 mPa·s or more at 25°C.

[0341] The base resin (C) may have a viscosity greater than 1,000,000 mPa·s. The base resin (C) may be semi-solid (semi-liquid) or solid. When the base resin (C) has a viscosity greater than 1,000,000 mPa·s, the resin composition containing the obtained powder particles has the advantages of less stickiness and easy handling.

[0342] The base resin (C) preferably has an endothermic peak at 25°C or lower in the thermogram of differential scanning calorimetry (DSC), and more preferably has an endothermic peak at 0°C or lower. With the above configuration, the base resin (C) has the advantage of excellent fluidity.

[0343] When the base resin (C) is a thermosetting resin, its state is not particularly limited as long as it is in a flowing state when mixed with the powder particles, and it may be solid at room temperature. From the viewpoint of operability, it is preferably liquid at room temperature.

[0344] (6-3. Mixing ratio, etc. of powder particles or dry powder and base resin (C))

[0345] Regarding the mixing ratio of this powder or granular material and the matrix resin (C), when the total of the powder or granular material and the matrix resin (C) is set to 100% by weight, it is generally preferred that the powder or granular material is 0.5 to 50% by weight and the matrix resin (C) is 50 to 99.5% by weight. More preferably, the powder or granular material is 1 to 35% by weight and the matrix resin (C) is 65 to 99% by weight. Particularly preferably, the powder or granular material is 1.5 to 25% by weight and the matrix resin (C) is 75 to 98.5% by weight. Most preferably, the powder or granular material is 2.5 to 20% by weight and the matrix resin is 80 to 97.5% by weight.

[0346] In order to make the ratio of the content of the polymer fine particles (A) and the matrix resin (C) in the obtained resin composition a desired value, the mixing ratio of this powder or granular material or the dry powder and the matrix resin (C) can be appropriately set according to (a) the content and moisture content of the components other than the polymer fine particles (A) contained in the powder or granular material or the dry powder, and (b) the mixing method of the powder or granular material or the dry powder and the matrix resin (C), etc.

[0347] Regarding the ratio of the content of the polymer fine particles (A) and the matrix resin (C) in the resin composition, when the total of the polymer fine particles (A) and the matrix resin (C) is set to 100% by weight, it is generally preferred that the polymer fine particles (A) are 0.5 to 50% by weight and the matrix resin (C) is 50 to 99.5% by weight. More preferably, the polymer fine particles (A) are 1 to 35% by weight and the matrix resin (C) is 65 to 99% by weight. Particularly preferably, the polymer fine particles (A) are 1.5 to 25% by weight and the matrix resin (C) is 75 to 98.5% by weight. Most preferably, the polymer fine particles (A) are 2.5 to 20% by weight and the matrix resin is 80 to 97.5% by weight.

[0348] The temperature when mixing the powder or granular material and the matrix resin (C) is usually set to the temperature at which the matrix resin (C) can flow. When the resin (B) can flow at the temperature at which the matrix resin (C) can flow, it becomes easy to uniformly mix the resin (B) and the matrix resin (C). On the contrary, when the matrix resin (C) is in a liquid state and the resin (B) in the powder or granular material to be added thereto is solid, it is difficult to uniformly mix the two. It should be noted that in this specification, the case where the matrix resin (C) is in a liquid state at 25°C is interpreted as "the viscosity of the matrix resin (C) at 25°C is equal to or higher than the viscosity of the resin (B) at 25°C".

[0349] (6-4. Organic solvents)

[0350] This resin composition preferably substantially does not contain an organic solvent. When the above-mentioned powder substantially does not contain an organic solvent, a resin composition substantially not containing an organic solvent can be obtained. "Substantially does not contain an organic solvent" means that the amount of the organic solvent in the resin composition is 100 ppm or less.

[0351] The amount of the organic solvent contained in this resin composition (also referred to as the solvent content) is preferably 100 ppm or less, more preferably 50 ppm or less, still more preferably 25 ppm or less, and particularly preferably 10 ppm or less. The amount of the organic solvent contained in this resin composition can also be said to be the amount of the volatile components (excluding water) contained in this resin composition. For the amount of the organic solvent (volatile component) contained in this resin composition, for example, a given amount of the resin composition can be heated with a hot air dryer or the like, and the weight of the resin composition before and after heating can be measured, so as to obtain it in the form of the reduced weight amount. In addition, the amount of the organic solvent (volatile component) contained in this resin composition can also be determined by gas chromatography. Furthermore, in the production of this resin composition and the powder contained in the resin composition, when no organic solvent is used, the amount of the organic solvent contained in the obtained resin composition can be regarded as 0 ppm.

[0352] Examples of the organic solvents that this resin composition substantially does not contain include: (a) esters such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate; (b) ketones such as acetone, methyl ethyl ketone, diethyl ketone, and methyl isobutyl ketone; (c) alcohols such as ethanol, (iso)propanol, and butanol; (d) ethers such as tetrahydrofuran, tetrahydropyran, dioxane, and diethyl ether; (e) aromatic hydrocarbons such as benzene, toluene, and xylene; and (f) halogenated hydrocarbons such as dichloromethane and chloroform.

[0353] (6-5. Other Optional Components)

[0354] This resin composition can contain other optional components as needed in addition to the above components. Examples of other optional components include: curing agents, coloring agents such as pigments and dyes, extender pigments, ultraviolet absorbers, antioxidants, heat stabilizers (gelation inhibitors), plasticizers, leveling agents, defoaming agents, silane coupling agents, antistatic agents, flame retardants, lubricants, viscosity reducers, low shrinkage agents, inorganic fillers, organic fillers, thermoplastic resins, desiccants, and dispersants.

[0355] This resin composition can further contain a known thermosetting resin other than the matrix resin, and can further contain a known thermoplastic resin.

[0356] [7. Cured Product]

[0357] In the resin composition described in [6. Resin Composition], a cured product obtained by curing a resin composition in which the above matrix resin (C) is a thermosetting resin is also an embodiment of the present invention. Hereinafter, the cured product of an embodiment of the present invention will also be simply referred to as the present cured product.

[0358] The present cured product (a) has a beautiful surface, (b) has high rigidity and a high elastic modulus, and (c) is excellent in toughness and adhesiveness.

[0359] [8. Other Uses]

[0360] The powder particles, granules, dry powders, the present powder particles, the present resin composition, or the cured product or molded article of the present resin composition produced by an embodiment of the present invention can be used for various purposes, and the uses are not particularly limited. The powder particles, granules, dry powders, the present powder particles, the present resin composition, or the cured product or molded article of the present resin composition produced by an embodiment of the present invention can be preferably used for, for example, adhesives, coating materials, adhesives for reinforcing fibers, composite materials, shaping materials for 3D printing, sealants, electronic substrates, ink adhesives, wood chip adhesives, adhesives for rubber sheets, adhesives for foamed sheets, adhesives for castings, bedrock consolidation materials for floor materials and ceramics, polyurethane foams, and the like. Examples of the polyurethane foam include: automobile seats, automobile interior parts, sound absorption materials, vibration damping materials, shock absorbers (impact absorption materials), heat insulation materials, buffer pads for engineering floor materials, and the like.

[0361] Among the above uses, the powder particles, granules, dry powders, the present powder particles, the present resin composition, or the cured product or molded article of the present resin composition produced by an embodiment of the present invention are more preferably used as adhesives, coating materials, adhesives for reinforcing fibers, composite materials, shaping materials for 3D printing, sealants, and electronic substrates.

[0362] (8-1. Adhesive)

[0363] The adhesive of an embodiment of the present invention contains the above present powder particles or resin composition. Since the adhesive of an embodiment of the present invention has the above constitution, it has excellent adhesiveness.

[0364] The adhesive of an embodiment of the present invention will also be simply referred to as the present adhesive.

[0365] The present adhesive can be preferably used for various purposes such as automobile interior material uses, general woodworking uses, furniture uses, interior decoration uses, wall material uses, and food packaging uses.

[0366] This adhesive shows good adhesion to various adherends such as panels made of cured thermosetting resins like cold-rolled steel, aluminum, glass fiber-reinforced polyester (FRP), carbon fiber-reinforced epoxy resin, panels made of carbon fiber-reinforced thermoplastic resin sheets, sheet molding compound (SMC), acrylonitrile-butadiene-styrene copolymer (ABS), polyvinyl chloride (PVC), polycarbonate, polypropylene, TPO, wood, and glass.

[0367] This adhesive not only has excellent adhesion performance and flexibility from low temperature (around -20°C) to normal temperature, but also at high temperature (around 80°C). Therefore, this adhesive can be preferably used as a structural adhesive.

[0368] The structural adhesive using this adhesive can be used, for example, as an adhesive for structural components in the fields of automobiles and locomotives (such as bullet trains, trams, etc.), civil engineering, construction, building materials, woodworking, electrical, electronics, aircraft, and aerospace industries. Especially for automotive-related uses, examples include the adhesion of interior materials such as the roof, doors, and seats, as well as the adhesion of exterior materials such as automotive lighting fixtures like lamps and side moldings.

[0369] This adhesive can be manufactured using this powder or resin composition. As the manufacturing method of this adhesive, there is no particular limitation, and known methods can be used.

[0370] (8 - 2. Coating material)

[0371] The coating material of one embodiment of the present invention contains the above-mentioned powder or resin composition. Since the coating material of one embodiment of the present invention has the above composition, a coating film with excellent load resistance and wear resistance can be provided.

[0372] The coating material of one embodiment of the present invention is also simply referred to as this coating material.

[0373] For example, when applying this coating material to a floor or corridor, the commonly implemented construction method can be applied. For example, after applying a primer to the surface-cleaned substrate, this coating material is evenly applied using a trowel, roller, rake, spray gun, etc. according to the construction conditions. After applying this coating material, curing is carried out to obtain a well-performing paving film. The coating film obtained by curing this coating material can be a coating film with excellent load resistance and wear resistance.

[0374] The viscosity of the resin composition used in this coating material can be adjusted according to the construction method of this coating material. For example, when a trowel or a rake is used in the construction of this coating material, the viscosity of the resin composition used in this coating material can usually be adjusted to about 500 to 9,000 cps / 25 °C. When a roller or a sprayer is used in the construction of this coating material, the viscosity of the resin composition used in this coating material can usually be adjusted to about 100 to 3,000 cps / 25 °C.

[0375] There is no particular limitation on the substrate (in other words, the material of the floor or corridor) coated with this coating material. Specifically, examples of the above substrate include: (a) inorganic substrates such as concrete walls, concrete slabs, concrete blocks, CMU (Concrete Masonry Unit), mortar boards, ALC (Autoclaved Light-weight Concrete) boards, gypsum boards (such as Dens Glass Gold manufactured by Georgia Pacific Corporation), and slate; (b) organic substrates such as wood substrates (wood, plywood, OSB (Oriented Strand Board), etc.), asphalt, modified asphalt waterproof sheets, ethylene-propylene-diene rubber (EPDM) waterproof sheets, TPO waterproof sheets, plastics, FRP, and polyurethane foam insulation materials; and (c) metal substrates such as metal panels.

[0376] The case of coating this coating material on a metal substrate or a porous substrate will be described. The laminate obtained by curing the coating material after the above coating is excellent in corrosion resistance to the above substrate. In addition, the coating film obtained by curing the coating material after the above coating can impart excellent crack resistance and load resistance to the substrate. Therefore, the method of coating this coating material on a metal substrate or a porous substrate is a particularly preferred method.

[0377] There is no particular limitation on the coating method of this coating material, and it can be carried out by known coating methods such as a trowel, a rake, a brush, a roller, an air sprayer, and a airless sprayer.

[0378] As for the uses of this coating material, there is no particular limitation, and examples include: automotive uses, electrical equipment uses, office equipment uses, building materials uses, wood uses, coated floor uses, paving uses, multiple anti-corrosion uses, concrete anti-corrosion uses, waterproof uses for platforms and roofs, corrosion-resistant uses for platforms and roofs, coating waterproof material uses for underground waterproofing, automotive repair uses, tank coating uses, topcoat uses, intermediate coat uses, primer coat uses, primer uses, electroplating coating uses, high weather-resistant coating uses, non-yellowing coating uses, etc. When used for coating materials for coated floors and paving materials, etc., it can be used in factories, laboratories, warehouses, and clean rooms, etc.

[0379] This coating material can be manufactured using this powder particle or resin composition. As the manufacturing method of this coating material, there is no particular limitation, and known methods can be used.

[0380] (8-3. Composite Material)

[0381] The composite material of one embodiment of the present invention contains the above-mentioned powder particle or resin composition as an adhesive for reinforcing fibers. Due to the above composition, the composite material of one embodiment of the present invention has the advantages of excellent toughness and impact resistance.

[0382] The composite material of one embodiment of the present invention is also simply referred to as this composite material.

[0383] This composite material may contain reinforcing fibers. As the above-mentioned reinforcing fibers, there is no particular limitation, and examples include: glass fibers, glass continuous fibers, carbon fibers, natural fibers, metal fibers, thermoplastic resin fibers, boron fibers, aramid fibers, polyethylene fibers, Zylon reinforcing fibers, etc. Among these reinforcing fibers, glass fibers and carbon fibers are particularly preferred.

[0384] As the manufacturing method (molding method) of this composite material, there is no particular limitation, and examples include: autoclave molding method using prepreg, filament winding molding method, hand lay-up molding method, vacuum bag molding method, resin transfer molding (RTM) method, vacuum assisted resin transfer molding (VARTM) method, pultrusion method, injection molding method, sheet winding molding method, spray molding method, BMC (Bulk Molding Compound) method, SMC (Sheet Molding Compound) method, etc.

[0385] Especially when carbon fibers are used as the reinforcing fibers, as the manufacturing method of this composite material, it is preferably used: autoclave molding method using prepreg, filament winding molding method, hand lay-up molding method, vacuum bag molding method, resin transfer molding (RTM) method, vacuum assisted resin transfer molding (VARTM) method, etc.

[0386] As for the uses of the present composite material, there is no particular limitation, and examples include: airplanes, spacecrafts, automobiles, bicycles, ships, weapons, windmills, sports goods, containers, building materials, waterproof materials, printed circuit boards, electrical insulating materials, etc.

[0387] The present composite material can be manufactured using the present powder particles or resin composition. For more detailed information regarding reinforcing fibers, manufacturing methods (molding methods), manufacturing conditions (molding conditions), compounding agents, uses, etc. related to the present composite material, reference can be made to the content described in U.S. Patent Publication No. 2006 / 0173128, U.S. Patent Publication No. 2012 / 0245286, Japanese Patent Application Laid-Open No. 2002-530445 (International Publication WO2000 / 029459), Japanese Patent Application Laid-Open No. 55-157620 (U.S. Patent No. 4251428), Japanese Patent Application Laid-Open No. 2013-504007 (International Publication WO2011 / 028271), Japanese Patent Application Laid-Open No. 2007-125889 (U.S. Patent Publication No. 2007 / 0098997), and Japanese Patent Application Laid-Open No. 2003-220661 (U.S. Patent Publication No. 2003 / 0134085).

[0388] (8-4. 3D Printing Forming Material)

[0389] The 3D printing forming material according to an embodiment of the present invention contains the above-mentioned present powder particles or resin composition. Since the 3D printing forming material according to an embodiment of the present invention has the above-mentioned constitution, it has the advantages of excellent toughness and impact resistance.

[0390] The 3D printing forming material according to an embodiment of the present invention is also simply referred to as the present forming material.

[0391] As for the uses of the present forming material, there is no particular limitation, and examples include: prototypes for the purpose of design verification and function verification before actual product production, components of airplanes, building components, and components of medical devices, etc.

[0392] The present forming material can be manufactured using the present powder particles or resin composition. As for the manufacturing method of the present forming material, there is no particular limitation, and known methods can be used.

[0393] (8-5. Sealant)

[0394] The sealant according to an embodiment of the present invention is made using the above-mentioned present powder particles or resin composition. Since the sealant according to an embodiment of the present invention has the above-mentioned constitution, it has the advantages of excellent toughness and impact resistance.

[0395] The sealant of an embodiment of the present invention is also simply referred to as the present sealant.

[0396] As the use of the present sealant, there is no particular limitation, and examples include sealing of various electrical devices such as semiconductors and power devices.

[0397] The present sealant can be manufactured using the present powder particles or resin composition. As the manufacturing method of the present sealant, there is no particular limitation, and known methods can be used.

[0398] (8 - 6. Electronic substrate)

[0399] The electronic substrate of an embodiment of the present invention is made of the above-mentioned present powder particles or resin composition. Since the electronic substrate of an embodiment of the present invention has the above-mentioned configuration, it has the advantages of excellent toughness and impact resistance.

[0400] The electronic substrate of an embodiment of the present invention is also simply referred to as the present electronic substrate.

[0401] As the use of the present electronic substrate, there is no particular limitation, and examples include: printed circuits, printed wirings, printed circuit boards, printed circuit actual installation products, printed wiring boards, and printed boards.

[0402] The present electronic substrate can be made of the present resin composition and manufactured from the present resin composition. As the manufacturing method of the present electronic substrate, there is no particular limitation, and known methods can be used.

[0403] An embodiment of the present invention may have the following configuration.

[0404] 〔1〕A method for manufacturing powder particles, the method comprising:

[0405] An impregnation step of impregnating a gas into a latex containing polymer particles; and

[0406] A spraying step of spraying the above-mentioned latex,

[0407] The above-mentioned polymer particles contain a graft copolymer having a graft portion.

[0408] 〔2〕The method for manufacturing powder particles according to 〔1〕, wherein

[0409] The above-mentioned impregnation step further has a pressurization step of applying a pressure of 0.5 MPa or more to the above-mentioned latex.

[0410] 〔3〕The method for manufacturing powder particles according to 〔1〕 or 〔2〕, which further includes:

[0411] A heating step of heating the above-mentioned latex before the above-mentioned spraying step.

[0412] 〔4〕The method for producing a powder or granular material according to 〔3〕, wherein

[0413] the heating temperature in the above-mentioned heating step is equal to or higher than the glass transition temperature of the above-mentioned graft portion.

[0414] 〔5〕The method for producing a powder or granular material according to any one of 〔1〕 to 〔4〕, wherein

[0415] the above-mentioned gas contains one or more selected from nitrogen, oxygen, and air.

[0416] 〔6〕The method for producing a powder or granular material according to any one of 〔1〕 to 〔5〕, wherein

[0417] based on the weight of the powder or granular material, the water content of the above-mentioned powder or granular material is 50% or more.

[0418] 〔7〕A method for producing granules, the method comprising:

[0419] a step of shaping the powder or granular material produced by the method for producing a powder or granular material according to any one of 〔1〕 to 〔6〕 into granules.

[0420] 〔8〕A method for producing a dry powder, the method comprising:

[0421] a step of drying the powder or granular material produced by the method for producing a powder or granular material according to any one of 〔1〕 to 〔6〕.

[0422] 〔9〕A powder or granular material which is a powder or granular material obtained by aggregating polymer fine particles,

[0423] the above-mentioned polymer fine particles (a) contain a graft copolymer having a graft portion, and (b) have a volume average particle diameter of 0.03 μm to 2.00 μm,

[0424] the disintegration rate of the above-mentioned powder or granular material is 5% or less,

[0425] wherein, the above-mentioned disintegration rate means: using a cylindrical drum with a diameter of 17 mm to compact the above-mentioned powder or granular material under a pressure of 100 kPa or more to produce a molded article, passing the molded article through a sieve with a mesh size of 4 mm, dividing the weight of the above-mentioned powder or granular material passing through the sieve by the weight of the above-mentioned molded article before sieving, and multiplying the obtained value by 100.

[0426] 〔10〕The powder or granular material according to 〔9〕, wherein

[0427] based on the weight of the powder or granular material, the water content of the above-mentioned powder or granular material is 50% or more.

[0428] 〔11〕The powder or granular material according to 〔9〕 or 〔10〕, wherein

[0429] When preparing a dispersion aqueous solution by dispersing the above-mentioned powder particles in water, in the dispersion aqueous solution, 90% by volume or more of the 100% by volume of the polymer particles contained in the powder particles are dispersed in the form of primary particles.

[0430]

[12] A particle comprising a powder particle formed by aggregating polymer particles

[0431] The above-mentioned polymer particles (a) contain a graft copolymer having a graft portion, and (b) have a volume average particle diameter of 0.03 μm to 2.00 μm.

[0432] The disintegration rate of the particle is 5% or less.

[0433] Among them, the above-mentioned disintegration rate means that when the above-mentioned particle is passed through a sieve with a mesh size of 4 mm, the weight of the above-mentioned powder particle passing through the sieve is divided by the weight of the above-mentioned particle before sieving, and the obtained value is multiplied by 100.

[0434] Examples

[0435] Hereinafter, one embodiment of the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited thereto. One embodiment of the present invention can be appropriately modified and implemented within the scope suitable for the above-mentioned or the following gist, and these are all included in the technical scope of the present invention. It should be noted that in the following examples and comparative examples, unless otherwise specified, "parts" means "parts by weight" and "%" means "% by weight".

[0436] [Evaluation method]

[0437] First, hereinafter, the evaluation method of the powder particles manufactured by examples and comparative examples will be described.

[0438] (Measurement of volume average particle diameter of elastomer and polymer particles (A))

[0439] The volume average particle diameter (Mv) of the elastomer or polymer particles (A) dispersed in the aqueous latex is measured using NanotracWaveII-EX150 (manufactured by MicrotracBEL Corporation). The latex obtained by diluting the aqueous latex with deionized water is used as the measurement sample. In the measurement, the refractive index of water and the elastomer or polymer particles (A) obtained in each production example are input, and the sample concentration is adjusted so that the measurement time is 120 seconds and the load index is in the range of 1 to 20.

[0440] (Recovery rate of polymer particles (A))

[0441] The recovery rate of the polymer particles (A) was calculated as described below. When the liquid latex was confirmed after the spraying process, the liquid latex was recovered, weighed, and the recovery rate was calculated according to the following formula. 1 - ((weight of the latex recovered in liquid form after the spraying process) / (weight of the latex introduced into the pressure vessel)) × 100

[0442] It should be noted that when the liquid latex was not confirmed after the spraying process, the recovery rate was 100%. The results of the recovery rate of the polymer particles (A) are shown in the column of "Recovery rate of polymer" in Table 1.

[0443] (Method for measuring the viscosity of resin (B))

[0444] The viscosity of resin (B) at 25 °C (i.e., the viscosity of resin (B) at 25 °C) was measured using a viscometer (DV2T, manufactured by Brookfield). A conical spindle was used during the measurement.

[0445] (Water content)

[0446] The water content of the powder was measured as described below. Using 5 g of the powder as a sample, the water content was measured with a heat drying type moisture meter (MX-50, manufactured by A&D). The set temperature was 105 °C. The water content was calculated by the following formula.

[0447] Water content (%) = {(amount of water) / (weight of the dried powder + amount of water)} × 100.

[0448] (Disintegration rate)

[0449] Using powders A, C, C', F, and J, a molded product was made and the disintegration rate of the molded product was measured. The specific method is as follows. 1 g of the powder was added to a plastic cylindrical drum with an inner diameter of 13 mm and a height of 17 mm. A load of 104 kPa was applied to the powder in the drum for 30 seconds using a plunger to make a molded product of the powder. Then, the molded product was placed on a plain sieve with a mesh size of 4 mm and a wire diameter of 1.4 mm. Classification was carried out by manually vibrating the sieve. Specifically, the sieve was grasped on both sides with both hands and moved horizontally to the left and right by 75 mm. Vibration was carried out at a speed of 20 times per 10 seconds (one round trip is one time) for 20 seconds. The weight of the powder that passed through the sieve was divided by the amount of the molded product before sieving (i.e., 1 g), and the value obtained was multiplied by 100 as the disintegration rate.

[0450] (Elemental analysis of the dried resin)

[0451] The concentrations of calcium and chlorine elements in the dried resins obtained in Example 4 and Comparative Example 4 were measured using a fluorescence X-ray analyzer (XEPOS SPECTRO).

[0452] (Calculation method of ΔYI before and after heat stability test)

[0453] Test pieces with a thickness of 2 mm were made using the powder particles obtained in Example 4 and Comparative Example 4. The test pieces were obtained as follows. The obtained powder particles were mixed with a polycarbonate resin at a ratio of powder particles: polycarbonate resin = 2:100, and the mixture was extruded and kneaded using a twin-screw extruder (TEX-44, manufactured by Japan Steel Works, Ltd.) and granulated. The molding conditions of the extruder were set as C2 - C9 = 260 °C and die head temperature = 260 °C. Then, the obtained granules were dried in a drying oven at 120 °C for 5 hours, and then an ASTM D638-1 type (dumbbell piece) test test piece was made using an injection molding machine (Model 160MSP-10, manufactured by Mitsubishi Heavy Industries, Ltd.). The injection molding conditions were set as barrel temperature T3 = 275 °C, T2 = 280 °C, T1 = 285 °C, nozzle temperature N = 285 °C, and mold temperature = 90 °C.

[0454] For the obtained test pieces, the hue / YI was measured in accordance with ASTM-E1925 using a color difference meter (Model: SE-2000) manufactured by Nippon Denshoku Industries Co., Ltd. Next, the test pieces were left standing in a drying oven at 120 °C for 6 days. Then, the hue / YI of the test pieces taken out from the drying oven was measured by the same method as above. The value of the hue / YI before the drying oven treatment was divided by the value of the hue / YI after the drying oven treatment to obtain ΔYI before and after the heat stability test. The smaller the ΔYI before and after the heat stability test, the better. A small ΔYI before and after the heat stability test means that the hue change is small when used in a high-temperature environment.

[0455] (Dispersibility A)

[0456] By the following method, the proportion of the polymer microparticles (A) contained in the powder particles in the dispersed aqueous solution that are dispersed in the form of primary particles was calculated. 0.5 g of the powder particle B obtained in Example 2 or the powder particle C obtained in Comparative Example 2 was mixed with 20 ml of water, and the mixture was stirred to prepare a dispersed aqueous solution. The obtained dispersed aqueous solution was used as a sample, and the volume-based particle size distribution of the polymer microparticles (A) dispersed in the dispersed aqueous solution was measured using a laser diffraction particle size distribution analyzer (LA-950 manufactured by Horiba, Ltd.) or a dynamic light scattering particle size distribution analyzer (Zetasizer ZSP manufactured by Malvern). Specifically, a dynamic light scattering particle size distribution analyzer (Zetasizer ZSP manufactured by Malvern) was used for the powder particle B of Example 2, and a laser diffraction particle size distribution analyzer (LA-950 manufactured by Horiba, Ltd.) was used for the powder particle C. Based on the obtained values, when the total of each sample was set to 100%, the cumulative volume frequency of the primary particles contained in each sample was expressed as the proportion of the polymer microparticles (A) dispersed in the form of primary particles. The results are shown in Figure 1 .

[0457] (Dispersibility B)

[0458] The degree of dispersion (dispersibility B) of the polymer microparticles (A) in the matrix resin (C) in the resin composition was evaluated by a method based on the evaluation method of JIS K 5600-2-5 (General test method for paints - Degree of dispersion). A particle size meter with a maximum cell depth of 100 μm was used in the evaluation. The specific evaluation method is as follows. The resin compositions obtained in Examples 5 and 6 were placed on the particle size meter, and the resin composition on the particle size meter was scraped off with a metal spatula, and the dispersion state was confirmed by visual observation. The scale at the position where 5 to 10 points were generated in a 3 mm-wide band of the granular marks generated by the movement of the spatula was read. The results are shown in Table 4.

[0459] Production Example: Preparation of Polymer Microparticles (A)

[0460] Production Example 1-1; Preparation of polybutadiene rubber latex (R-1) (Polymerization of elastomer)

[0461] In a pressure-resistant polymerizer equipped with a stirrer, 200 parts of pure water, 0.03 part of tripotassium phosphate, 0.0012 part of ferrous sulfate heptahydrate, 0.008 part of disodium ethylenediaminetetraacetate (EDTA), and 0.03 part of sodium polyoxyethylene alkyl ether phosphate were charged. Then, while stirring the charged raw materials, the gas inside the pressure-resistant polymerizer was replaced with nitrogen, thereby sufficiently removing oxygen from the inside of the pressure-resistant polymerizer. Then, 100 parts of butadiene (Bd), 0.05 part of sodium formaldehyde sulfoxylate (SFS), and 0.2 part of para-menthane hydroperoxide (PHP) were charged into the pressure-resistant polymerizer. Then, 1.4 parts of sodium polyoxyethylene alkyl ether phosphate were dropwise added to the pressure-resistant polymerizer over 6 hours. Then, the reaction solution inside the pressure-resistant polymerizer was maintained at a pH of 6.5 to 7.5 and a temperature of 50 °C for 10 hours to carry out polymerization. The conversion rate was 98% by weight. Through this polymerization, an aqueous latex (R-1) containing an elastomer mainly composed of polybutadiene rubber was obtained. The volume average particle diameter of the elastomer contained in the obtained aqueous latex was 140 nm.

[0462] Production Example 1-2; Preparation of Polymer Particle Latex (L-1) (Polymerization of Graft Portion)

[0463] The above polybutadiene rubber latex (R-1) was charged into a glass reactor to an amount equivalent to about 71 parts of solid content. Here, the above glass reactor has a thermometer, a stirrer, a reflux condenser, a nitrogen gas inlet, and a monomer addition device. The gas in the glass reactor was replaced with nitrogen, and the charged raw materials were stirred at 60 °C. Then, while maintaining the pH of the reaction solution in the glass reactor at 6.5 to 7.5 and the temperature of the reaction solution at about 60 °C, (a) 22 parts of methyl methacrylate (MMA) and 7 parts of styrene (St) were continuously added to the glass reactor over 60 minutes, and (b) the total amount of 0.07 part of tert-butyl hydroperoxide (BHP) and 0.1 part of SFS was added to the glass reactor over 2 hours to carry out polymerization. The addition of MMA and St started simultaneously with the addition of BHP and SFS. After adding the total amount of BHP and SFS, the reaction solution was further maintained at about 60 °C for 1 hour to end the polymerization. Through this polymerization, a latex (L-1) containing polymer particles (A) was obtained. The latex (L-1) is an aqueous latex. The volume average particle diameter of the polymer particles (A) contained in the obtained latex was 200 nm. The solid content concentration in the obtained latex was 37%.

[0464] Production Example 1-3; Preparation of Polybutadiene Rubber Latex (R-2) (Polymerization of Elastomer)

[0465] In a pressure-resistant polymerizer equipped with a stirrer, 200 parts of deionized water, 0.03 part of tripotassium phosphate, 0.002 part of EDTA, 0.001 part of ferrous sulfate heptahydrate, and 1.55 parts of sodium dodecylbenzenesulfonate (SDBS) were charged. Then, while stirring the charged raw materials, the gas inside the pressure-resistant polymerizer was replaced with nitrogen, thereby sufficiently removing oxygen from the inside of the pressure-resistant polymerizer. Then, 100 parts of Bd was charged into the pressure-resistant polymerizer, and the temperature inside the pressure-resistant polymerizer was raised to 45°C. Then, 0.03 part of PHP was charged into the pressure-resistant polymerizer, and then 0.10 part of SFS was charged into the pressure-resistant polymerizer to initiate polymerization. At the 15th hour from the initiation of polymerization, devolatilization was carried out under reduced pressure to remove the monomers remaining unused during polymerization, thereby ending the polymerization. During the polymerization, PHP, EDTA, and ferrous sulfate heptahydrate were added to the pressure-resistant polymerizer in arbitrary amounts and at arbitrary times. Through this polymerization, a latex (R-2) containing an elastomer having polybutadiene rubber as a main component was obtained. The latex (R-2) was an aqueous latex. The volume average particle diameter of the elastomer contained in the obtained latex was 90 nm.

[0466] Production Example 1-4; Preparation of polybutadiene rubber latex (R-3) (Polymerization of elastomer)

[0467] In a pressure-resistant polymerizer, 7 parts by solid content of the above-obtained polybutadiene rubber latex (R-2), 200 parts of deionized water, 0.03 part of tripotassium phosphate, 0.002 part of EDTA, and 0.001 part of ferrous sulfate heptahydrate were charged. Then, while stirring the charged raw materials, the gas inside the pressure-resistant polymerizer was replaced with nitrogen, thereby sufficiently removing oxygen from the inside of the pressure-resistant polymerizer. Then, 93 parts of Bd was charged into the pressure-resistant polymerizer, and the temperature inside the pressure-resistant polymerizer was raised to 45°C. Then, 0.02 part of PHP was charged into the pressure-resistant polymerizer, and then 0.10 part of SFS was charged into the pressure-resistant polymerizer to initiate polymerization. At the 30th hour from the initiation of polymerization, devolatilization was carried out under reduced pressure to remove the monomers remaining unused during polymerization, thereby ending the polymerization. During the polymerization, PHP, EDTA, and ferrous sulfate heptahydrate were added to the pressure-resistant polymerizer in arbitrary amounts and at arbitrary times. Through this polymerization, a latex (R-3) containing an elastomer having polybutadiene rubber as a main component was obtained. The latex (R-3) was an aqueous latex. The volume average particle diameter of the elastomer contained in the obtained latex was 195 nm.

[0468] Production Example 1-5; Preparation of polymer particle latex (L-2) (Polymerization of graft portion)

[0469] Into a glass reactor, 215 parts of the above polybutadiene rubber latex (R-3) (including 70 parts of an elastomer having polybutadiene rubber as the main component) and 82 parts of deionized water were charged. Here, the above glass reactor has a thermometer, a stirrer, a reflux condenser, a nitrogen gas inlet, and a monomer addition device. The gas in the glass reactor was replaced with nitrogen, and the charged raw materials were stirred at 60°C. Next, 2.6 parts of 1,3-butanediol dimethacrylate and 0.007 parts of tert-butyl hydroperoxide (BHP) were added to the glass reactor, and the mixture in the glass reactor was stirred for 10 minutes. Then, 0.004 parts by weight of EDTA, 0.001 parts by weight of ferrous sulfate heptahydrate, and 0.13 parts of SFS were added to the glass reactor and stirred for 30 minutes. Then, 0.013 parts of BHP were added to the glass reactor and stirred for 30 minutes.

[0470] Then, a mixture of 28.5 parts of MMA, 1.5 parts of butyl acrylate (BA), and 0.085 parts of BHP was continuously added to the glass reactor over 120 minutes. Then, 0.013 parts of BHP were added to the glass reactor, and the mixture in the glass reactor was continuously stirred for 1 hour to complete the polymerization. Through the above operations, a latex (L-2) containing polymer particles (A) was obtained. The polymerization conversion rate of the monomer components was 99% or more. The latex (L-2) was an aqueous latex. The volume average particle diameter of the polymer particles (A) contained in the obtained latex was 200 nm. The solid content concentration (concentration of polymer particles (A)) in the obtained latex (L-2) was 31%.

[0471] (Example 1)

[0472] (Impregnation step and heating step)

[0473] Relative to 2000 g of the latex (L-1), 2 parts of IRGANOX-1076 [n-octadecyl 3-(3’,5’-di-tert-butyl-4’-hydroxyphenyl) propionate], a phenolic antioxidant, were added, and the obtained latex was charged into a pressure vessel equipped with a stirrer. After the pressure vessel was sealed, the latex was heated while stirring the latex, and the temperature of the latex was raised to 130°C. When the temperature of the latex reached 130°C, nitrogen was introduced into the pressure vessel, and the pressure of the gas phase part in the pressure vessel was pressurized to 3.0 MPa, and a pressure of 3.0 MPa was applied to the latex (L-1). The state where the temperature of the latex was 130°C and the pressure of the gas phase part in the pressure vessel was 3.0 MPa was maintained for 5 minutes. By this operation, a gas containing nitrogen was impregnated into the latex (L-1).

[0474] (Spraying step)

[0475] A ball valve and a flow path with an orifice having a diameter of φ2.8 mm are installed at the discharge port of the above-mentioned pressure vessel. After the above-mentioned impregnation process and heating process are completed, the above-mentioned ball valve is opened, and the latex in the pressure vessel is introduced into the above-mentioned flow path, and the latex impregnated with gas is sprayed (ejected) through the above-mentioned orifice. Thus, powdery particles with a water content of 60% are obtained. The obtained powdery particles are used as powdery particles A. The recovery rate of the polymer particles (A) is shown in Table 1. A molded product is made using the powdery particles A, and the disintegration rate of the molded product is measured, and the results are shown in Table 2. It should be noted that the molded product of the powdery particles A can be regarded as the particles of an embodiment of the present invention.

[0476] (Example 2)

[0477] (Impregnation process and heating process)

[0478] Relative to 2000 g of latex (L-1), 2 parts of IRGANOX-1076 [n-octadecyl 3-(3’,5’-di-tert-butyl-4’-hydroxyphenyl) propionate], which is a phenolic antioxidant, is added, and the obtained latex is put into a pressure vessel equipped with a stirrer. After the pressure vessel is sealed, the latex is heated while stirring the latex, and the temperature of the latex is raised to 130°C. When the temperature of the latex reaches 130°C, carbon dioxide gas is introduced into the pressure vessel, and the pressure of the gas phase part in the pressure vessel is pressurized to 3.0 MPa, and a pressure of 3.0 MPa is applied to the latex (L-1). The state where the temperature of the latex is 130°C and the pressure of the gas phase part in the pressure vessel is 3.0 MPa is maintained for 5 minutes. Through this operation, the gas containing carbon dioxide is impregnated into the latex (L-1).

[0479] (Spraying process)

[0480] A ball valve and a flow path with an orifice having a diameter of φ2.8 mm are installed at the discharge port of the above-mentioned pressure vessel. After the above-mentioned impregnation process and heating process are completed, the above-mentioned ball valve is opened, and the latex in the pressure vessel is introduced into the above-mentioned flow path, and the latex impregnated with gas is sprayed (ejected) through the above-mentioned orifice. Thus, powdery particles with a water content of 62% are obtained. The obtained powdery particles are used as powdery particles B. The recovery rate of the polymer particles (A) is shown in Table 1. A dispersion aqueous solution is made using the powdery particles B, and the proportion of the polymer particles (A) dispersed in the form of primary particles in the polymer particles (A) contained in the powdery particles B in the dispersion aqueous solution is measured by the method described in the above (Dispersibility A). The results are shown by a solid black line in Figure 1 .

[0481] (Example 3)

[0482] (Impregnation process and heating process)

[0483] With respect to 2000 g of latex (L-1), 2 parts of IRGANOX-1076 [n-octadecyl 3-(3’,5’-di-tert-butyl-4’-hydroxyphenyl) propionate], which is a phenolic antioxidant, were added, and the resulting latex was put into a pressure vessel equipped with a stirrer. After closing the pressure vessel, the latex was heated while stirring, and the temperature of the latex was raised to 130 °C. The stirring of the latex continued until the spraying of the latex was completed. When the temperature of the latex reached 130 °C, air was introduced into the pressure vessel, and the pressure in the gas phase part of the pressure vessel was pressurized to 3.0 MPa, and a pressure of 3.0 MPa was applied to the latex (L-1). The state where the temperature of the latex was 130 °C and the pressure in the gas phase part of the pressure vessel was 3.0 MPa was maintained for 5 minutes. By this operation, the gas (air) was impregnated into the latex (L-1).

[0484] (Spraying process)

[0485] A flow path provided with a ball valve and an orifice with a diameter of φ2.8 mm was installed at the discharge port of the above pressure vessel. After the above impregnation process and heating process were completed, the above ball valve was opened, the latex in the pressure vessel was introduced into the above flow path, and the latex impregnated with gas was sprayed (ejected) through the above orifice. Thus, a powdery particle with a moisture content of 63% was obtained. The recovery rate of the polymer particles (A) is shown in Table 1.

[0486] (Comparative Example 1)

[0487] (Impregnation process and heating process)

[0488] With respect to 2000 g of latex (L-1), 2 parts of IRGANOX-1076 [n-octadecyl 3-(3’,5’-di-tert-butyl-4’-hydroxyphenyl) propionate], which is a phenolic antioxidant, were added, and the resulting latex was put into a pressure vessel equipped with a stirrer. After closing the pressure vessel, the latex was heated while stirring, and the temperature of the latex was raised to 130 °C. When the temperature of the latex reached 130 °C, carbon dioxide was introduced into the pressure vessel, and the pressure in the gas phase part of the pressure vessel was pressurized to 3.0 MPa. The state where the temperature of the latex was 130 °C and the pressure in the gas phase part of the pressure vessel was 3.0 MPa was maintained for 5 minutes.

[0489] (Spraying process)

[0490] A flow path with a ball valve is installed at the discharge port of the above-mentioned pressure vessel. After the above-mentioned impregnation process and heating process are completed, the heating of the latex is ended, and the latex is naturally cooled to 75 °C. Then, the above-mentioned ball valve is opened, and the latex in the pressure vessel is introduced into the above-mentioned flow path, and the latex is ejected at normal pressure through the above-mentioned orifice. That is, in Comparative Example 1, the latex was not sprayed. In Comparative Example 1, after the latex was ejected, no powder particles were obtained, but a latex in which the polymer particles (A) were not aggregated was obtained. The thinly film-coated latex was recovered from the inner wall surface of the pressure vessel, and the recovery rate was calculated using it. The recovery rates are shown in Table 1.

[0491] [Table 1]

[0492]

[0493] As can be seen from Table 1, according to the manufacturing method of one embodiment of the present invention, the polymer particles (A) can be efficiently recovered from the latex.

[0494] (Comparative Example 2)

[0495] Relative to 1000 g of latex (L-1), 2 parts of IRGANOX-1076 [n-octadecyl 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate], a phenolic antioxidant, was added. An aqueous calcium chloride solution was added to the obtained latex to obtain an aggregate of polymer particles (A). The obtained aggregate was heat-treated at 95 °C for 5 minutes. For the obtained aggregate, the aggregate was washed with 400 parts of pure water. Then, the aggregate was subjected to dehydration to obtain white powder particles. The obtained powder particles were used as powder particles C. A molded article was produced using powder particles C, and the disintegration rate of the molded article was measured. The results are shown in Table 2. In addition, a dispersion aqueous solution was prepared using powder particles C, and the proportion of polymer particles (A) dispersed in the form of primary particles in the polymer particles (A) contained in powder particles C in the dispersion aqueous solution was measured by the method described in the above (Dispersibility A). The results are shown by a gray long dashed line in Figure 1 .

[0496] (Comparative Example 3)

[0497] Pure water was added to the powder particles C obtained in Comparative Example 2 to adjust the moisture content of the powder particles, and powder particles C' with a moisture content of 58% was obtained. A molded article was produced using powder particles C', and the disintegration rate of the molded article was measured. The results are shown in Table 2.

[0498] [Table 2]

[0499] Powder Water content Disintegration rate Example 1 Powder A 58％ 1％ Comparative Example 2 Powder C 35％ 79％ Comparative Example 3 Powder C’ 58％ 48％

[0500] As can be seen from Table 2, according to the comparison between Example 1 and Comparative Example 2, the disintegration rate of the powder particles obtained by this manufacturing method is lower than that of the powder particles obtained by the existing manufacturing method. In addition, according to the comparison between Example 1 and Comparative Example 3, even when the powder particles obtained by the existing manufacturing method are adjusted to have the same moisture content as the powder particles obtained by this manufacturing method, the disintegration rate of the powder particles obtained by this manufacturing method is lower than that of the powder particles obtained by the existing manufacturing method. That is, it can be considered that compared with the powder particles obtained by the existing manufacturing method, the generation of fine powder of the powder particles obtained by this manufacturing method is less, and the moldability is more excellent.

[0501] Next, the volume average particle size distribution (volume-based particle size distribution) of the polymer particles (A) dispersed in the dispersion aqueous solution of the powder particles B obtained in Example 2 or the dispersion aqueous solution of the powder particles C obtained in Comparative Example 2 is shown by a solid black line or a long dashed gray line in Figure 1 . In addition, using the latex (L-1) containing polymer particles, the volume average particle size distribution of the polymer particles (A) dispersed in the latex (L-1) was measured in the same manner as the above dispersion aqueous solution, and the result is shown by a black dotted line in Figure 1 . The volume average particle size distribution of the polymer particles (A) dispersed in the latex (L-1) can be considered as the volume average particle size distribution of the primary particles of the polymer particles (A).

[0502] According to Figure 1 the results, in the dispersion aqueous solution of the powder particles B, 99% of the polymer particles (A) contained in the powder particles B are dispersed in the form of primary particles in 100% by volume of the polymer particles (A). On the other hand, in the dispersion aqueous solution of the powder particles C, 0% of the polymer particles (A) contained in the powder particles C are dispersed in the form of primary particles in 100% by volume of the polymer particles (A).

[0503] (Example 4)

[0504] (Manufacture of dry powder)

[0505] The powder particles A were left standing in a dryer at 50 °C to dry the powder particles A, and a dry resin D in the form of a white powder was obtained. The dry resin D was washed with 400 parts of water, and the washed dry resin D was left standing in a dryer at 50 °C to obtain a dry resin D' in the form of a white powder. The elemental analysis of the dry resin and ΔYI before and after the thermal stability test were measured using the dry resin D and the dry resin D'. The results are shown in Table 3. It should be noted that the dry resins D and D' can be considered as the dry powders of one embodiment of the present invention.

[0506] (Comparative Example 4)

[0507] (Manufacture of Dry Powder)

[0508] The powder granule C was left still in a dryer at 50°C to dry the powder granule C, and a dry resin E in the form of a white powder was obtained. The dry resin E was washed with 400 parts of water, and the washed dry resin E was left still in a dryer at 50°C to obtain a dry resin E' in the form of a white powder. Using the dry resin E and the dry resin E', elemental analysis of the dry resin and ΔYI before and after the thermal stability test were measured. The results are shown in Table 3.

[0509] [Table 3]

[0510]

[0511] ※<The symbol indicates below the lower limit of measurement.

[0512] From Table 3, it can be seen that compared with the dry resin obtained in Comparative Example 4, the dry resins (dry resin D and dry resin D') obtained in Example 4 have less calcium and chlorine elements in the dry resin regardless of whether they are washed. On the other hand, it can be seen that compared with the dry resin obtained in Example 4, the dry resin (dry resin E') obtained in Comparative Example 4 contains a very large amount of calcium and chlorine elements despite being washed. In addition, compared with the dry resin obtained in Comparative Example 4, the dry resin obtained in Example 4 has a lower ΔYI before and after the thermal stability test. Therefore, it can be considered that when used under high-temperature conditions, the dry resin (dry powder) obtained by drying the powder granule by this manufacturing method is more stable than the dry resin (dry powder) obtained by the prior art.

[0513] (Example 5)

[0514] (Resin Mixing Process, Impregnation Process and Heating Process)

[0515] To 333 parts of latex (L-2) equivalent to 100 parts of polymer particles (A), 8.8 parts by weight (equivalent to 5.3 parts by weight of epoxy resin) of (a) liquid epoxy resin aqueous emulsion W2821R70 (manufactured by Mitsubishi Chemical Corporation, solid content concentration 70% by weight, epoxy resin content 60%, viscosity (700 mPa·s, 25°C)) as resin (B) and 1.1 parts by weight of (b) IRGANOX 1135 (octyl 3-(4-hydroxy-3,5-diisopropylphenyl)propionate) (manufactured by BASF JAPAN Co., Ltd.) were mixed to obtain a latex containing polymer particles (A) and resin (B). The obtained latex was put into a pressure-resistant container (total volume about 2 L) equipped with a stirrer. After sealing the pressure-resistant container, the latex was heated while stirring the latex to raise the temperature of the latex to 130°C. When the temperature of the latex reached 130°C, nitrogen was introduced into the pressure-resistant container, and the pressure in the gas phase part of the pressure-resistant container was pressurized to 3.0 MPa to apply a pressure of 3.0 MPa to the latex. The state where the temperature of the latex was 130°C and the pressure in the gas phase part of the pressure-resistant container was 3.0 MPa was maintained for 5 minutes. By this operation, a gas containing nitrogen was impregnated into the latex containing resin (B).

[0516] (Spraying process)

[0517] A flow path provided with a ball valve and an orifice with a pore diameter of φ2.8 mm was installed at the discharge port of the above-mentioned pressure-resistant container. After the above-mentioned impregnation process and heating process were completed, the ball valve was opened, the latex in the pressure-resistant container was introduced into the above-mentioned flow path, and the latex impregnated with gas was sprayed (ejected) through the above-mentioned orifice. Thus, a powdery substance with a moisture content of 64% was obtained. The obtained powdery substance was designated as powdery substance F. The recovery rate of polymer particles (A) is shown in Table 4. A molded article was produced using powdery substance F, and the disintegration rate of the molded article was measured, and the results are shown in Table 4. It should be noted that the molded article of powdery substance F can be regarded as a particle of an embodiment of the present invention.

[0518] (Manufacture of dry powder)

[0519] The obtained powdery substance F was left in a dryer at 50°C to dry the powdery substance F to obtain a dry resin G1 as a white powdery dry powder. The following operations (i) to (iii) were carried out twice in sequence to wash the dry resin G1 to obtain a resin G2: (i) 500 parts of ion-exchanged water was added to the dry resin G1; (ii) the obtained mixture was stirred; (iii) water was removed from the obtained mixture. The washed resin G2 was left in a dryer at 50°C to dry the resin G2 to obtain a dry resin G3 as a white powdery dry powder. It should be noted that the dry resins G1 and G3 are dry powders of an embodiment of the present invention.

[0520] (Manufacture of Resin Composition)

[0521] The obtained dried resin G3 (dried powder) and bisphenol A epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER828) as the matrix resin (C) were put into the container of a planetary mixer (ARE-310, manufactured by THINKY Corporation) in a weight ratio (weight of dried resin G3: weight of bisphenol A epoxy resin) of 5:95. The raw materials in the container were mixed by this planetary mixer at a rotational speed of 2000 rpm for 40 minutes to obtain a resin composition H. The evaluation results of the dispersibility B of the obtained resin composition H are shown in Table 4.

[0522] (Example 6)

[0523] (Impregnation Process and Heating Process)

[0524] Approximately 2 L of latex (L-2) equivalent to 100 parts of polymer particles (A) was put into a pressure-resistant container equipped with a stirrer. After sealing the pressure-resistant container, the latex was heated while stirring to raise the temperature of the latex to 130°C. When the temperature of the latex reached 130°C, nitrogen was introduced into the pressure-resistant container, and the pressure in the gas phase part of the pressure-resistant container was pressurized to 3.0 MPa to apply a pressure of 3.0 MPa to the latex (L-2). The state where the temperature of the latex was 130°C and the pressure in the gas phase part of the pressure-resistant container was 3.0 MPa was maintained for 5 minutes. Through this operation, a gas containing nitrogen was impregnated into the latex (L-2).

[0525] (Spraying Process)

[0526] A flow path equipped with a ball valve and an orifice with a diameter of φ2.8 mm was installed at the discharge port of the above pressure-resistant container. After the above impregnation process and heating process were completed, the ball valve was opened, and the latex in the pressure-resistant container was introduced into the above flow path, and the gas-impregnated latex was sprayed (ejected) through the above orifice. Thus, a powder particle with a moisture content of 65% was obtained. The obtained powder particle was designated as powder particle J. The recovery rate of polymer particles (A) is shown in Table 4. A molded article was made using powder particle J, and the disintegration rate of the molded article was measured, and the results are shown in Table 4. It should be noted that the molded article of powder particle J can be regarded as a particle of an embodiment of the present invention.

[0527] (Manufacture of Dried Powder)

[0528] The obtained powder J was left still in a dryer at 50 °C to dry the powder J, and a dried resin K1 as a white powdery dried powder was obtained. The following operations (i) to (iii) were performed twice in sequence to wash the dried resin K1, and a resin K2 was obtained: (i) 500 parts of ion-exchanged water was added to the dried resin K1; (ii) the obtained mixture was stirred; (iii) water was removed from the obtained mixture. The washed resin K2 was left still in a dryer at 50 °C to dry the resin K2, and a dried resin K3 as a white powdery dried powder was obtained. It should be noted that the dried resins K1 and K3 are the dried powders of one embodiment of the present invention.

[0529] (Manufacture of resin composition)

[0530] The obtained dried resin K3 (dried powder) and bisphenol A epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER828) as a matrix resin (C) were put into a container of a planetary mixer (ARE-310, manufactured by THINKY Corporation) so that the weight ratio (weight of dried resin K3: weight of bisphenol A epoxy resin) was 5:95. The raw materials in the container were mixed by this planetary mixer at a rotational speed of 2000 rpm for 40 minutes to obtain a resin composition L. The evaluation results of the dispersibility B of the obtained resin composition L are shown in Table 4.

[0531] [Table 4]

[0532]

[0533] As shown in Table 4, the recovery rate of the polymer particles (A) in the form of powder in Examples 5 and 6 was 100%, and the moisture content was substantially the same value. In addition, the disintegration rates of Examples 5 and 6 were substantially the same values and were both within the range of one embodiment of the present application. On the other hand, it can be seen that the dispersibility of the powder in Example 5 containing the resin (B) was more excellent than that of the powder in Example 6 not containing the resin (B).

[0534] Industrial applicability

[0535] According to one embodiment of the present invention, polymer particles can be recovered from a latex containing polymer particles without using an electrolyte and an organic solvent. Thus, a powder with low inclusions (low impurities) and a small environmental burden can be obtained. A resin composition containing the powder obtained by one embodiment of the present invention or a cured product obtained by curing the resin composition can be suitably used for uses such as adhesives, coating materials, adhesives for reinforcing fibers, composite materials, shaping materials for 3D printing, sealants, and electronic substrates.

Claims

1. A method for manufacturing a powder or granular material, the method comprising: An impregnation step of impregnating a gas into a latex containing polymer particles; and A spraying step of spraying the latex, wherein the polymer particles contain a graft copolymer having a graft portion.

2. The method for manufacturing a powder or granular material according to claim 1, wherein, The impregnation step further has a pressurizing step of applying a pressure of 0.5 MPa or more to the latex.

3. The method for manufacturing a powder or granular material according to claim 1 or 2, further comprising: A heating step of heating the latex before the spraying step.

4. The method for manufacturing a powder or granular material according to claim 3, wherein, The heating temperature in the heating step is equal to or higher than the glass transition temperature of the graft portion.

5. The method for manufacturing a powder or granular material according to claim 1 or 2, wherein, The gas contains one or more selected from nitrogen, oxygen, and air.

6. The method for manufacturing a powder or granular material according to claim 1 or 2, wherein, Based on the weight of the powder, the water content of the powder is 50% or more.

7. A method for manufacturing a granule, the method comprising: A step of molding the powder obtained by the method for producing a powder according to any one of claims 1 to 6 into granules.

8. A method for manufacturing a dry powder, the method comprising: A step of drying the powder obtained by the method for producing a powder according to any one of claims 1 to 6.

9. A powder or granular material, which is a powder or granular material manufactured by the method for manufacturing a powder or granular material according to any one of claims 1 to 6, the polymer microparticles (a) comprise a graft copolymer having a graft portion, and (b) have a volume average particle diameter of 0.03 μm to 2.00 μm, the disintegration rate of the powder or granular material is 5% or less, wherein, The disintegration rate means that a molded product is produced by compacting the powder at a pressure of 100 kPa or more using a cylindrical drum with a diameter of 17 mm, and when the molded product is passed through a sieve with a mesh size of 4 mm, the weight of the powder passing through the sieve is divided by the weight of the molded product before sieving, and the value obtained is multiplied by 100. Based on the weight of the powder, the water content of the powder is 50% or more.

10. The powder or granular material according to claim 9, wherein, When the powder is dispersed in water to prepare a dispersion aqueous solution, in the dispersion aqueous solution, 90% by volume or more of the 100% by volume of the polymer particles contained in the powder are dispersed in the form of primary particles.

11. A granule, which is a powder or granular material manufactured by the method for manufacturing a granule according to claim 7, the polymer microparticles (a) comprise a graft copolymer having a graft portion, and (b) have a volume average particle diameter of 0.03 μm to 2.00 μm, the disintegration rate of the granule is 5% or less, wherein, The disintegration rate means that when the granule is passed through a sieve with a mesh size of 4 mm, the weight of the powder passing through the sieve is divided by the weight of the granule before sieving, and the value obtained is multiplied by 100. Based on the weight of the powder, the water content of the powder is 50% or more.

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