Polymer particle group containing polyorganosiloxane, composition, resin composition, and molded body

Abstract

The polymer particle group containing polyorganosiloxane involved in this invention comprises a polymer (A) containing polyorganosiloxane (A1) and a first vinyl polymer (A2) and a second vinyl polymer (B). When the cross-section of a resin sheet obtained by dispersing the polymer particle group containing polyorganosiloxane in a resin is observed with a transmission electron microscope, the diameter of each particle of the polymer particle group containing polyorganosiloxane is set to L, and the maximum length of the polyorganosiloxane (A1) region is set to M. The ratio of the number of particles satisfying the following formula (1) is less than 60%. M / L>0.1···(1).

Description

Technical Field

[0001] This invention relates to polymer particle groups, compositions, resin compositions, and molded articles containing polyorganosiloxanes.

[0002] This application claims priority based on Japan Patent Application No. 2020-102397 filed on June 12, 2020, the contents of which are incorporated herein by reference. Background Technology

[0003] Rubber-containing polymers, formed by polymerizing vinyl monomers and rubbery polymers, can be dispersed in a wide variety of resins while maintaining a specified rubber particle size and structure, making them suitable for resins requiring impact strength.

[0004] Generally, considering the improvement of impact strength, rubber polymers with low elastic modulus and high Poisson's ratio are preferred. Butadiene rubber and silicone rubber have an extremely high Poisson's ratio of 0.5 and a low elastic modulus, making them suitable for use as rubber polymers.

[0005] Among them, silicone rubbers, compared with butadiene rubbers, are less prone to curing or discoloration caused by heat or ultraviolet light, exhibiting excellent durability. Therefore, they are suitable for applications requiring long-term maintenance of mechanical properties, such as building materials or automotive parts. Polyorganosiloxanes, represented by polydimethylsiloxane, can be used as silicone rubbers.

[0006] However, polysiloxanes are more expensive than butadiene rubber. Furthermore, when polysiloxane-containing polymers are mixed with resins (such as polycarbonate, polymethyl methacrylate, and styrene-acrylonitrile copolymers) that have a higher refractive index compared to polysiloxane polymers, the resulting molded articles exhibit reduced transparency, making it difficult to achieve a colored appearance, particularly deep and rich color tones.

[0007] Patent Document 1 describes a resin composition containing various thermoplastic resins such as vinyl chloride resin, polycarbonate resin, and polyester resin, and a graft copolymer containing a polyorganosiloxane. In Patent Document 1, the pigment colorability of the resulting molded article is improved by making the number average particle size of the polyorganosiloxane graft copolymer 5 to 80 nm and making the volume of particles larger than 100 nm less than 10% of the total particle volume.

[0008] Patent Document 2 describes a resin composition containing a styrene-acrylonitrile copolymer and a graft copolymer containing a polyorganosiloxane. Furthermore, it describes a graft copolymer containing a polyorganosiloxane with a weight-average particle size of 110 nm or less.

[0009] Patent document 3 describes a resin composition containing polymethyl methacrylate resin and a graft copolymer containing polyorganosiloxane.

[0010] Existing technical documents

[0011] Patent documents

[0012] [Patent Document 1] Japanese Patent Application Publication No. 6-116471

[0013] [Patent Document 2] Japanese Patent Application Publication No. 2009-155421

[0014] [Patent Document 3] Japanese Patent Application Publication No. 2000-327880 Summary of the Invention

[0015] The technical problem that the invention aims to solve

[0016] However, in any existing technology, there is a problem that the impact strength of the resulting molded article is insufficient.

[0017] The purpose of this invention is to provide a group of polyorganosiloxane polymer particles, compositions, and resin compositions that can produce molded articles with excellent impact strength.

[0018] Another object of the present invention is to provide a molded article with excellent impact strength.

[0019] means of solving technical problems

[0020] The present invention has the following aspects.

[0021] [1] A group of polymer particles containing a polyorganosiloxane is a group of polymer particles containing a polymer (A) and a second vinyl polymer (B), wherein the polymer (A) comprises a polyorganosiloxane (A1) and a first vinyl polymer (A2).

[0022] When the cross-section of the resin sheet obtained by dispersing the polymer particle group containing the polyorganosiloxane in the resin is observed by a transmission electron microscope, the diameter of each particle of the polymer particle group containing the polyorganosiloxane is set as L, and the maximum length of the polyorganosiloxane (A1) region is set as M, the proportion of particles that satisfy the following formula (1) is less than 60%.

[0023] M / L>0.1···(1)

[0024] [2] According to the polymer particle group containing polyorganosiloxane described in [1], the ratio of the polyorganosiloxane (Al) to 100% by mass of the polymer particle group containing polyorganosiloxane is more than 1% by mass and less than 50% by mass.

[0025] [3] The ratio of the polyorganosiloxane (Al) to the polymer particle group containing the polyorganosiloxane according to [1] or [2] is more than 1% by mass and less than 10% by mass relative to 100% by mass of the polymer particle group containing the polyorganosiloxane.

[0026] [4] The polymer particle group containing polyorganosiloxane according to any one of [1] to [3] has a number average particle size of 10 nm or more and 150 nm or less.

[0027] [5] The polymer particle group containing polyorganosiloxane according to any one of [1] to [4], wherein a portion of each particle of the polymer particle group containing polyorganosiloxane is insoluble in tetrahydrofuran, and the ratio of the polymer particle group containing polyorganosiloxane that is insoluble in tetrahydrofuran to 100% by mass of the polymer particle group containing polyorganosiloxane is 80% by mass or more but less than 100% by mass.

[0028] [6] The polymer particle group containing polyorganosiloxane according to any one of [1] to [5], wherein a portion of each particle of the polymer particle group containing polyorganosiloxane is soluble in tetrahydrofuran, and the weight-average molecular weight of the polymer particle group containing polyorganosiloxane soluble in tetrahydrofuran is more than 20,000 and less than 500,000.

[0029] [7] When the cross-section of the resin sheet is observed by a transmission electron microscope, the polymer (A) of the polymer particle group containing polyorganosiloxane according to any one of [1] to [6] has an island structure in which the polyorganosiloxane (A1) is a sea component and the first vinyl polymer (A2) is an island component.

[0030] In the island structure, the polyorganosiloxane (A1) region contains a plurality of the first vinyl polymer (A2) regions.

[0031] [8] When the cross-section of the resin sheet is observed by a transmission electron microscope, each particle of the polymer particle group containing the polyorganosiloxane according to any one of [1] to [7] has an island structure in which the polyorganosiloxane (A1) is used as the sea component, the first vinyl polymer (A2) is used as the first island component, and the second vinyl polymer (B) is used as the second island component.

[0032] [9] The polymer (A) of any one of the polymer particle groups containing polyorganosiloxanes according to any one of [1] to [8] is 60% by mass or more and 95% by mass or less relative to 100% by mass of the polymer particle group containing polyorganosiloxanes.

[0033]

[10] The group of polymer particles containing polyorganosiloxane according to any one of [1] to [9], wherein the vinyl monomer component (a2) constituting the first vinyl polymer (A2) contains a monofunctional (meth)acrylate monomer.

[0034]

[11] The group of polymer particles containing polyorganosiloxane according to any one of [1] to

[10] , wherein the vinyl monomer component (b) constituting the second vinyl polymer (B) contains at least one selected from the group consisting of (meth)acrylate monomers and aromatic vinyl monomers,

[0035] The total ratio of the (meth)acrylate monomer and the aromatic vinyl monomer is 50% or more relative to 100% by mass of the vinyl monomer component (b).

[0036]

[12] The group of polymer particles containing polyorganosiloxane according to any one of [1] to

[11] , wherein the vinyl monomer component (b) constituting the second vinyl polymer (B) contains methyl methacrylate,

[0037] The ratio of methyl methacrylate to the vinyl monomer component (b) is 50% by mass or more.

[0038]

[13] The group of polymer particles containing polyorganosiloxane according to any one of [1] to

[12] , wherein the polymer (A) is a polymer formed by polymerizing the vinyl monomer component (a2) constituting the first vinyl polymer (A2) in the presence of a latex containing the polyorganosiloxane (A1).

[0039]

[14] A composition comprising a group of polymer particles containing polyorganosiloxane as described in any one of [1] to

[13] , and at least one component selected from the group consisting of phosphoric acid compounds and their alkali metal salts.

[0040]

[15] According to the composition of

[14] , the alkali metal salt of the phosphoric acid compound is at least one selected from the group consisting of alkali metal salts of alkyl phosphoric acid and alkali metal salts of alkylaryl phosphoric acid.

[0041]

[16] According to the composition of

[14] or

[15] , wherein the alkali metal salt of the phosphoric acid compound is an alkali metal salt of polyoxyalkylene ether phosphoric acid.

[0042]

[17] The composition according to any one of

[14] to

[16] contains at least 100 ppm of phosphorus atoms in the total mass of the polymer particle group containing the polyorganosiloxane and at least one component selected from the group consisting of the phosphoric acid compound and its alkali metal salt.

[0043]

[18] A resin composition comprising a group of polymer particles containing polyorganosiloxane as described in any one of [1] to

[13] and a thermoplastic resin.

[0044]

[19] A resin composition comprising the composition described in any one of

[14] to

[17] and a thermoplastic resin.

[0045]

[20] According to the resin composition of

[18] or

[19] , the thermoplastic resin contains at least one selected from the group consisting of aromatic polycarbonate, polymethyl methacrylate, styrene-acrylonitrile copolymer, polyethylene terephthalate, polybutylene terephthalate, polyvinyl chloride, polyphenylene sulfide and polyacetal.

[0046]

[21] A molded body containing a group of polymer particles containing polyorganosiloxane as described in any one of [1] to

[13] .

[0047] The effects of the invention

[0048] According to the polymer particle group containing polyorganosiloxane of the present invention, molded articles with excellent impact strength can be obtained.

[0049] The composition according to the present invention can yield molded articles with excellent impact strength.

[0050] According to the resin composition of the present invention, molded articles with excellent impact strength can be obtained.

[0051] The molded article of this invention has excellent impact strength. Attached Figure Description

[0052] [ Figure 1 [Image] is a transmission electron microscope (TEM) image of the composite particle swarm (C-1) manufactured in [Example].

[0053] [ Figure 2 [Image] is a brightness image resolution image of the transmission electron microscope (TEM) image of the composite particle swarm (C-1) manufactured in [Example].

[0054] [ Figure 3 [Image] is a brightness image resolution image of the transmission electron microscope (TEM) image of the composite particle swarm (C-3) manufactured in [Example].

[0055] [ Figure 4 [Image] is a brightness image resolution image of the transmission electron microscope (TEM) image of the composite particle swarm (C-4) manufactured in [Example].

[0056] [ Figure 5[Image] is a brightness image resolution image of the transmission electron microscope (TEM) image of the composite particle swarm (C-6) manufactured in [Example].

[0057] [ Figure 6 [Image] is a brightness image resolution image of the transmission electron microscope (TEM) image of the composite particle swarm (C-7) manufactured in [Example].

[0058] [ Figure 7 [Image] is a brightness image resolution image of the transmission electron microscope (TEM) image of the composite particle swarm (C-8) manufactured in [Example].

[0059] [ Figure 8 [Image] is a brightness image resolution image of the transmission electron microscope (TEM) image of the composite particle swarm (C-11) manufactured in [Example].

[0060] [ Figure 9 [Image] is a brightness image resolution image of the transmission electron microscope (TEM) image of the composite particle swarm (C-12) manufactured in [Example].

[0061] [ Figure 10 [Image] is a brightness image resolution image of the transmission electron microscope (TEM) image of the composite particle swarm (C-13) manufactured in [Example].

[0062] [ Figure 11 [Image] is a brightness image resolution image of the transmission electron microscope (TEM) image of the composite particle swarm (C-14) manufactured in [Example].

[0063] [ Figure 12 [Image] is a brightness image resolution image of the transmission electron microscope (TEM) image of the composite particle swarm (C-15) manufactured in [Example].

[0064] [ Figure 13 [Image] is a brightness image resolution image of the transmission electron microscope (TEM) image of the composite particle swarm (C-17) manufactured in [Example].

[0065] [ Figure 14 [Image] is a brightness image resolution image of the transmission electron microscope (TEM) image of the composite particle swarm (C-18) manufactured in [Example].

[0066] [ Figure 15 [Image] is a brightness image resolution image of the transmission electron microscope (TEM) image of the composite particle swarm (C-19) manufactured in [Example].

[0067] [ Figure 16[Image] is a brightness image resolution image of the transmission electron microscope (TEM) image of the composite particle swarm (C-20) manufactured in [Example]. Detailed Implementation

[0068] The embodiments of the present invention will now be described in detail.

[0069] In this invention, the vinyl monomer is a compound having polymerizable double bonds.

[0070] “(Meth)acrylate” refers to acrylate or methacrylate.

[0071] In this manual, the term "transmission electron microscope" will also be referred to as "TEM".

[0072] [Polymer particle clusters containing polyorganosiloxanes]

[0073] One embodiment of the present invention relates to a group of polymer particles containing a polyorganosiloxane (hereinafter also referred to as "polymer particle group (C)") comprising a polymer (A) and a second vinyl polymer (B) (hereinafter also referred to as "vinyl polymer (B)"). Polymer (A) comprises a polyorganosiloxane (A1) and a first vinyl polymer (A2) (hereinafter also referred to as "vinyl polymer (A2)").

[0074] Polyorganosiloxane (A1), vinyl polymer (A2), polymer (A), and vinyl polymer (B) will be described in detail later.

[0075] Typically, each particle in a polymer particle group (C) contains a polymer (A) and a vinyl polymer (B).

[0076] The polymer particle group (C) is defined as the proportion of particles (hereinafter also referred to as "Z value") that satisfy the following formula (1) when the cross-section of the resin sheet obtained by dispersing the polymer particle group (C) in the resin is observed by TEM, with the diameter (μm) of each particle of the polymer particle group (C) set as L and the maximum length (μm) of the polyorganosiloxane (A1) region set as M.

[0077] M / L>0.1···(1)

[0078] When the Z-value is less than 60%, the molded articles containing polymer particle clusters (C) exhibit excellent impact strength, color appearance, and weather resistance. The Z-value is preferably 50% or less, more preferably 30% or less, further preferably 20% or less, and particularly preferably 10% or less. A smaller Z-value is better, and there is no particular limitation on the lower limit.

[0079] Preferably, when the cross-section of the resin sheet is observed using TEM, the polymer particle cluster (C) has an island structure, in which the polyorganosiloxane (A1) is the sea component and the vinyl polymer (A2) is the island component. As described above, by employing an island structure composed of polyorganosiloxane (A1) and vinyl polymer (A2), the molded body containing the polymer particle cluster (C) exhibits superior impact strength, color appearance, and weather resistance.

[0080] When observing the cross-section of the resin sheet using TEM, each particle in the polymer particle group (C) preferably has an island structure with polyorganosiloxane (A1) as the sea component, vinyl polymer (A2) as the first island component, and vinyl polymer (B) as the second island component. With this composite island structure of polyorganosiloxane (A1), vinyl polymer (A2), and vinyl polymer (B), the molded article exhibits superior impact strength and color appearance.

[0081] As described above, the island structure composed of polyorganosiloxane (A1), vinyl polymer (A2) and vinyl polymer (B) can be formed, for example, by impregnating at least a portion of the vinyl monomer component (b) constituting the vinyl polymer (B) into the polymer (A) and polymerizing it during the manufacture of the polymer particle group (C).

[0082] In order to impregnate at least a portion of the vinyl monomer component (b) in the polymer (A), for example, it is sufficient that at least a portion of the vinyl monomer component (b) uses a vinyl monomer with a solubility of less than 1.0 g / L in water at 30°C.

[0083] Examples of vinyl monomers with a solubility of less than 1.0 g / L in water at 30°C include styrene, alkyl-substituted styrene, alkyl-substituted isopropylbenzene, and 1,1-diphenylethylene, which are vinyl monomers described later.

[0084] Methods for distinguishing between the first island component and the second island component include, for example, elemental analysis using TEM observation with adjusted staining conditions (specifically, the type of staining agent and staining time), energy-dispersive X-ray spectrometry, and electron energy loss spectroscopy.

[0085] Each particle in the polymer particle group (C) may contain a vinyl polymer (B) that does not form a second island component. The vinyl polymer (B) that does not form a second island component (a vinyl polymer (B) polymerized without the vinyl monomer component (b) impregnated in polymer (A)) exists on the outer surface of polymer (A) as a graft polymer (a polymer covalently bonded to polymer (A)) or a free polymer (a polymer physically adsorbed to polymer (A) rather than covalently bonded).

[0086] Specifically, the cross-sectional TEM image of the aforementioned resin sheet can be obtained in the following order.

[0087] (1) First, the polymer particle group (C) is placed at the front end of the polyethylene capsule, and liquid uncured epoxy resin is injected. The capsule is then left to stand at 25°C for 12 hours to cure, resulting in a resin sheet.

[0088] (2) Next, the obtained resin sheet was stained with an osmium tetroxide aqueous solution (23°C, 12 hours).

[0089] (3) Next, the resin slides stained with osmium tetroxide aqueous solution were stained with ruthenium tetroxide aqueous solution (23°C, 5 hours).

[0090] (4) Next, slices were cut from the resin slide stained with ruthenium tetroxide aqueous solution using a microtome and recycled onto a copper grid with a support film. The thickness of the slices was set to 50 nm.

[0091] (5) Next, the surface (cross-section of the resin sheet) of randomly selected slices was obtained by TEM. 2 Images within the above range (TEM images). The image magnification is set to 200,000x.

[0092] In the obtained TEM image, such as Figure 1 As shown, the epoxy resin cured product region (hereinafter also referred to as the "resin region") is observed as the continuous phase, and the regions of individual particles of the polymer particle group (C) (hereinafter also referred to as the "particle regions") are observed as the dispersed phase dispersed within the resin region. Additionally, in the TEM image, as... Figure 1 As shown, the polysiloxane (A1) region (hereinafter also referred to as the "polysiloxane (A1) domain") in the particle region is identified with light contrast, and the vinyl polymer (A2) or vinyl polymer (B) region (hereinafter also referred to as the "vinyl polymer domain") is identified with dark contrast.

[0093] in addition, Figure 1 The “TEM image” is a TEM image of the polymer particle swarm (C-1) produced in the embodiments described later.

[0094] like Figure 2 As shown, particle regions, polyorganosiloxane (A1) regions, and vinyl polymer regions can be extracted from the obtained TEM images using image analysis software (such as ImageJ).

[0095] Specifically, for TEM images, the contrast of particle regions is extracted through line profile measurement. In line profile measurement, the maximum Ferrette diameter of a particle region can be set as the major axis and the minimum Ferrette diameter as the minor axis. A line is drawn by cutting off the particle size through the intersection of the major and minor axes (hereinafter also referred to as the "center point"). When the maximum and minimum Ferrette diameters are the same, multiple lines representing the same Ferrette diameter can be arbitrarily determined, and the center point is obtained from their intersection. In addition, the lines are drawn such that their ends do not connect with adjacent particle regions. The length of the drawn line is set as the diameter L of the particle region. In addition, although lines can be drawn arbitrarily where the above-mentioned conditions are met, it is preferable to draw multiple lines in a particle region, and use the line with the maximum value of the ratio (hereinafter also referred to as the "M / L value") between the diameter L of the particle region and the maximum length M of the polyorganosiloxane (Al) region obtained by the method described later for the line profile of that particle region. When drawing multiple lines, first draw an arbitrary first line. Then draw a second line whose angle (below 90°) at the midpoint with the first line is between 30° and 60°. Next, draw a third line perpendicular to the second line at the midpoint. Evaluate all three lines and select the one that represents the largest M / L value. However, if multiple lines satisfying the above criteria cannot be drawn, the M / L value obtained by evaluating fewer than three lines can be used.

[0096] At this point, since the particle region that meets the following criteria cannot be identified as a single particle, it is not selected as the particle region for measuring the line profile.

[0097] (i) Particle regions truncated at the edges of the image.

[0098] (ii) Particle regions with a size less than 80% of the average particle size.

[0099] (iii) A particle region that has adjacent particle regions in three or more directions, and whose boundaries are unclear.

[0100] All remaining particle regions that can be identified in the image are measured, and line profiles are measured for a total of 50 or more particle regions. If more than 50 particle regions that do not conform to (i) to (iii) above cannot be measured in a single TEM image, measurements are performed and summed based on multiple TEM images obtained from different fields of view.

[0101] The average particle size in (ii) above is the average of the equivalent circle diameter of the particle region that can be identified in the image.

[0102] Then, the distance from one end to the other of the line drawn in the particle region is set as the horizontal axis (X-axis), and the contrast (Gray Value) on the line is plotted as the Y-value as the vertical axis (Y-axis). The maximum value of the Y-value and the value of 75% of the maximum value (set as YA value) in a particle region are calculated. Regions with Y values ​​greater than YA value are defined as HGV regions. Here, since the brighter (lighter) the color, the larger the Y value, the polysiloxane (A1) region is identified using light contrast, and the vinyl polymer region is identified using dark contrast, thus enabling the differentiation between HGV regions and polysiloxane (A1) regions.

[0103] The region with the maximum continuous length within a particle region of the HGV region is defined as the maximum region of polyorganosiloxane (A1) within that particle region, and the continuous length of this HGV region is set as the maximum length M of the region. Here, the continuous length of the HGV region refers to the length of the line drawn with the YA value among the peaks where the gray value exceeds the YA value. Figure 2 The distance between the intersection points (represented by dashed lines in the middle).

[0104] In the particle region where the line profile was measured, the number of particle regions that satisfy the above formula (1) is set as Z1, and the number of particle regions that do not satisfy the above formula (1) is set as Z2. The Z value is calculated according to the following formula (2).

[0105] Z-value = {Z1 / (Z1+Z2)} × 100···(2)

[0106] Figure 2 In this context, "TEM image" refers to the TEM image obtained for the polymer (C-1) manufactured in the examples described later, and the image in ImageJ was used to measure the line profile.

[0107] Figure 2 In the example, "Analysis Example" is an example of graphically representing and analyzing the results of line profile determination of polymer (C-1) using ImageJ.

[0108] In the "Analysis Example," to facilitate a simple comparison of particle regions with different particle sizes, an example is shown where the length of the line (diameter L) is converted to 1. This will be discussed later. Figures 3-16 The same applies to China.

[0109] In the aforementioned island structure, the average diameter of the vinyl polymer domains is preferably 50 nm or less, more preferably 30 nm or less, and particularly preferably 20 nm or less. If the average diameter of the vinyl polymer domains is 50 nm or less, the impact strength of the molded article is superior.

[0110] There is no particular lower limit to the average diameter of the vinyl polymer domain, for example, 2 nm.

[0111] In the aforementioned island structure, from the viewpoint of the impact strength of the molded article, it is preferable to contain a plurality of vinyl polymer domains within the polyorganosiloxane (A1) domain. Furthermore, the average diameter of the vinyl polymer domains is preferably 50 nm or less, more preferably 30 nm or less. The lower limit of the average diameter of the vinyl polymer (A2) domains is not particularly limited, for example, it is 2 nm.

[0112] The vinyl polymer domain can be the region of vinyl polymer (A2) alone, or it can be both the region of vinyl polymer (A2) and the region of vinyl polymer (B).

[0113] When the vinyl polymer domain is only a region of vinyl polymer (A2), the average diameter of the vinyl polymer domain is the average diameter of the vinyl polymer (A2) region.

[0114] The average diameter of the vinyl polymer domains can be confirmed by various methods, such as from the TEM images described above. Specifically, it can be confirmed by following these steps.

[0115] First, obtain a TEM image through the steps described above.

[0116] Next, from the obtained TEM image, image analysis software (e.g., Image-Pro Plus, manufactured by Roper Co., Ltd., Japan) is used to extract the particle region, polysiloxane (A1) region, and vinyl polymer region, respectively. Specifically, for the TEM image, after flattening and denoising the background brightness unevenness, binarization is performed using the maximum unselected brightness of the surrounding resin region as the boundary, which allows for the extraction of the particle region, polysiloxane (A1) region, and vinyl polymer region, respectively.

[0117] From the large particle regions, select at least 30% and more than 100 confirmed particle regions as the measurement targets. The selected particle region ratio refers to the ratio of the number of selected particle regions to the total number of particle regions in the image with an equivalent circle diameter of 10 nm or more.

[0118] For each particle region of the selected measurement object, among the vinyl polymer domains existing within that region, vinyl polymer domains with an equivalent circular diameter of 10 nm or greater are selected, and the average value of the equivalent circular diameters of these vinyl polymer domains is taken as the average diameter. Alternatively, the average value of the average diameters calculated for all particle regions of the measurement object can be used as the average diameter of the vinyl polymer domains.

[0119] The ratio of polyorganosiloxane (A1) to the polymer particle group (C) is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, even more preferably 20% by mass or less, particularly preferably 10% by mass or less, most preferably 6% by mass or less, and on the other hand, preferably 1% by mass or more. If the ratio of polyorganosiloxane (A1) is above the lower limit, the impact strength of the molded article is better, and if it is below the upper limit, the color appearance of the molded article is better.

[0120] The ratio of polymer (A) to polymer particle cluster (C) is preferably 60% by mass or more, more preferably 65% ​​by mass or more, and on the other hand, preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less. If the content of polymer (A) is at or above the lower limit mentioned above, the impact strength of the molded article is better, and if it is at or below the upper limit mentioned above, the dispersibility of polymer particle cluster (C) in the thermoplastic resin is better, and the appearance of the resulting molded article is better.

[0121] The ratio of polymer (A) to polymer particle group (C) in 100% mass can be, for example, 60-95% mass, 60-90% mass, 65-90% mass, or 65-85% mass.

[0122] The ratio of vinyl polymer (B) to polymer particle cluster (C) is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more. On the other hand, it is preferably 40% by mass or less, more preferably 35% by mass or less. If the content of vinyl polymer (B) is at or above the lower limit mentioned above, the dispersibility of polymer particle cluster (C) in the thermoplastic resin is better, and the appearance of the resulting molded article is better. If it is at or below the upper limit mentioned above, the impact strength of the molded article is better.

[0123] The ratio of vinyl polymer (B) to polymer particle group (C) in 100% by mass can be, for example, 5-40% by mass, 10-40% by mass, 10-35% by mass, or 15-35% by mass.

[0124] Typically, a portion of the individual particles in the polymer particle group (C) is insoluble in tetrahydrofuran (hereinafter also referred to as "THF"). In other words, a portion of the individual particles in the polymer particle group (C) is soluble in THF.

[0125] Hereinafter, the portion of each particle in the polymer particle group (C) that is insoluble in THF will be referred to as the "THF insoluble component", and the portion that is soluble in THF will be referred to as the "THF soluble component".

[0126] The ratio of THF-insoluble component to 100% by mass of polymer particle cluster (C) is preferably 80% by mass or more, more preferably 85% by mass or more, further preferably 90% by mass or more, particularly preferably 93% by mass or more, and on the other hand, preferably less than 100% by mass, more preferably 99% by mass or less. If the ratio of THF-insoluble component is above the above-mentioned lower limit, the dispersibility of polymer particle cluster (C) in thermoplastic resin is better, and the impact strength and appearance of the resulting molded article are better. If the ratio of THF-insoluble component is less than 100% by mass, the balance between impact strength and color development is better, and if it is 99% by mass or less, the melt flowability when added to thermoplastic resin is better.

[0127] The ratio of THF insoluble components to 100% by mass of polymer particle group (C) can be 80% by mass or more but less than 100% by mass, 85% by mass or more but less than 100% by mass, 90% by mass or more but less than 99% by mass, or 93% by mass or more but less than 99% by mass.

[0128] The insoluble components of THF were determined by performing the following procedures (1-1) to (1-5).

[0129] (1-1) Add 0.5g of sample (polymer particle group (C)) to 50mL (44.5g) of THF to prepare a mixed solution. After standing at 25℃ for 8 hours, stir with a stirrer for 30 minutes to dissolve the THF soluble components.

[0130] (1-2) Place the mixed solution into a centrifuge tube for measuring mass, and centrifuge the liquid containing THF insoluble components and THF soluble components using a centrifuge (16000 rpm, 4 hours).

[0131] (1-3) After removing the supernatant, add THF back in and stir. Then, centrifuge again in the same way as (1-2) above to wash away the THF-insoluble components.

[0132] (1-4) Repeat (1-3) twice and remove the supernatant. Immerse the centrifuge tube containing the THF-insoluble component in a warm water bath (80°C, 8 hours) to allow the THF to evaporate. Then, vacuum dry at 65°C for 6 hours to obtain a dried sample (the THF-insoluble component adhering to the centrifuge tube).

[0133] (1-5) Determine the mass of the obtained dried sample (THF insoluble component + centrifuge tube), and calculate the ratio w of the THF insoluble component using the following formula. ais (%).

[0134] w ais =(w c1 -w as) / wt×100

[0135] wt: Mass of the polymer particle group (C) used in the determination

[0136] w as quality of centrifuge tubes

[0137] w c1 Mass of THF-insoluble components (including the mass of the centrifuge tube).

[0138] From the viewpoint of ensuring that the ratio of THF-insoluble components in the polymer particle group (C) is within the aforementioned range, it is preferable that the vinyl polymer (A2) is sufficiently crosslinked, and that the polyorganosiloxane (A1) is covalently bonded to the vinyl polymer (A2). Furthermore, it is preferable that the vinyl polymer (B) is covalently bonded to the polymer (A).

[0139] The weight-average molecular weight of the THF-soluble component of the polymer particle group (C) is preferably 20,000 or more, more preferably 50,000 or more, and on the other hand, preferably 500,000 or less, more preferably 350,000 or less, even more preferably 200,000 or less, and particularly preferably 150,000 or less.

[0140] If the weight-average molecular weight of the THF-soluble component is between 20,000 and 500,000, the polymer particle cluster (C) exhibits excellent dispersibility in the thermoplastic resin, resulting in molded articles with excellent impact strength and appearance. Specifically, if the weight-average molecular weight of the THF-soluble component is between 50,000 and 150,000, the polymer particle cluster (C) exhibits particularly good dispersibility in the thermoplastic resin, and under a wide range of molding conditions, including low mixing levels, the resulting molded articles also demonstrate excellent impact strength and appearance.

[0141] The weight-average molecular weight of the THF-soluble component of the polymer particle group (C) can be above 20,000 and below 500,000, above 20,000 and below 350,000, above 50,000 and below 200,000, or above 50,000 and below 150,000.

[0142] The weight-average molecular weight of the THF soluble component was determined by performing the following operations (2-1) to (2-3).

[0143] (2-1) THF is removed from the liquid containing THF soluble components collected by measuring the ratio of the above-mentioned THF insoluble components by vacuum distillation using a rotary evaporator to obtain the THF soluble components.

[0144] (2-2) Dissolve the THF soluble component obtained in (2-1) again in THF to make the sample concentration 0.1-0.3% by mass, and obtain a THF solution containing the THF soluble component.

[0145] (2-3) The THF solution containing the THF soluble component obtained in (2-2) above was determined by gel permeation chromatography (GPC), and the weight-average molecular weight (Mw) was determined from the quantitative curve of standard polystyrene.

[0146] The GPC measurement conditions are as described in the examples below.

[0147] The weight-average molecular weight of the THF-soluble component can be adjusted by the initiator dosage, reduction dosage, polymerization temperature, and the use of chain transfer agent when polymerizing the vinyl monomer component (b) constituting the vinyl polymer (B). For example, the weight-average molecular weight of the THF-soluble component can be reduced by increasing free radical generation caused by increasing the initiator dosage, reduction dosage, or polymerization temperature, or by promoting chain transfer reactions caused by the addition of chain transfer agent and the increase in the amount added.

[0148] The number-average particle size of the polymer particle cluster (C) is preferably 10 nm or more, more preferably 30 nm or more, further preferably 50 nm or more, particularly preferably 70 nm or more, and on the other hand, preferably 800 nm or less, more preferably 500 nm or less, more preferably 200 nm or less, particularly preferably 150 nm or less, particularly preferably 130 nm or less, and most preferably 100 nm or less. If the number-average particle size is above or below the above-mentioned lower limit, the impact strength of the molded article is better, and if it is below or below the above-mentioned upper limit, the color appearance of the molded article is better.

[0149] The number-average particle size of the polymer particle group (C) can be, for example, 10–800 nm, 30–500 nm, 50–200 nm, 50–150 nm, 70–130 nm, or 70–100 nm.

[0150] There are no particular limitations on the method for determining the number-average particle size of polymer particle groups (C), and it can be determined by, for example, the following methods.

[0151] The latex of polymer particle group (C) was diluted with deionized water to a concentration of about 3% as a sample. The particle size distribution based on the number of particles was determined using a capillary particle size analyzer (CHDF2000 particle size analyzer manufactured by MATEC Corporation, USA). The median diameter was used as the number-average particle size.

[0152] Particle size distribution can be determined under the following standard conditions recommended by MATEC.

[0153] Cartridge: A dedicated capillary cartridge for particle separation (trade name: C-202).

[0154] Carrier fluid: Dedicated carrier fluid (trade name: 2XGR500)

[0155] Liquidity of carrier liquid: Neutral

[0156] Flow rate of the carrier fluid: 1.4 ml / min

[0157] Carrier fluid pressure: approximately 4,000 psi (2,600 kPa)

[0158] Measurement temperature: 35℃

[0159] Sample volume used: 0.1 ml

[0160] In addition, as a standard particle size material, 12 types of monodisperse polystyrene with known particle sizes, manufactured by DUKE Corporation of the United States and ranging from 40 to 800 nm, can be used.

[0161] The number-average particle size of the polymer particle group (C) can be adjusted, for example, by the amount of emulsifier when the polymer particle group (C) is manufactured by emulsion polymerization.

[0162] (Polyorganosiloxane (A1))

[0163] Polyorganosiloxanes (A1) are polymers containing organosiloxane units. Polyorganosiloxanes (A1) can be obtained by polymerizing mixtures of organosiloxanes containing organosiloxanes. These organosiloxane mixtures may also contain components used as needed.

[0164] As an ingredient to be used as needed, at least one can be selected from the group consisting of siloxane crosslinking agents, siloxane crosslinking agents and siloxane oligomers with end capping groups.

[0165] Examples of organosiloxanes include chain-like organosiloxanes, alkoxysilane compounds, and cyclic organosiloxanes. Among these, alkoxysilane compounds and cyclic organosiloxanes are preferred. In particular, cyclic organosiloxanes are preferred due to their high polymerization stability and fast polymerization rate.

[0166] As alkoxysilane compounds, difunctional alkoxysilane compounds are preferred, such as dimethyldimethoxysilane, dimethyldiethoxysilane, diethoxydiethylsilane, dipropoxydimethylsilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, and methylphenyldiethoxysilane. They can be used alone or in combination of two or more.

[0167] As cyclic organosiloxanes, substances with 3 to 7-membered rings are preferred, such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, and octaphenylcyclotetrasiloxane. They can be used alone or in combination of two or more. Among these, octamethylcyclotetrasiloxane is preferred for ease of controlling particle size distribution.

[0168] From the viewpoint of obtaining a group of polymer particles (C) that can increase the impact strength of the molded body, at least one of the group consisting of cyclic dimethylsiloxane and 2-functional dialkylsilane compounds is preferred as the organosiloxane.

[0169] Cyclic dimethylsiloxanes are cyclic siloxanes having two methyl groups on a silicon atom. Examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecylcyclohexylsiloxane. They can be used alone or in combination of two or more.

[0170] 2. Functional dialkylsilane compounds refer to silane compounds having two alkoxy groups and two alkyl groups on a silicon atom. Examples include dimethyldimethoxysilane, dimethyldiethoxysilane, diethoxydiethylsilane, and dipropoxydimethylsilane. They can be used alone or in combination of two or more.

[0171] As a siloxane-based crosslinking agent, a crosslinking agent having a siloxane group is preferred. Examples of siloxane-based crosslinking agents include trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, and tetrabutoxysilane, which are trifunctional or tetrafunctional silane crosslinking agents. Among these, tetrafunctional crosslinking agents are preferred, and tetraethoxysilane is more preferred.

[0172] The ratio of the siloxane-based crosslinking agent to the organosiloxane mixture is preferably 10% by mass or less, more preferably 5% by mass or less, and may also be 0% by mass. If the content of the siloxane-based crosslinking agent is 10% by mass or less, a polymer particle group (C) that can improve the impact strength of the molded article can be obtained.

[0173] Siloxane-based crosslinkers have a siloxane group (-Si-O-) and functional groups capable of polymerizing with vinyl monomers. Examples of siloxane-based crosslinkers include siloxanes represented by the following formula (I).

[0174] R-Si(R 1 ) n (OR 2 ) (3-n) (I)

[0175] In equation (I), R 1 Indicates methyl, ethyl, propyl, or phenyl. R 2 This represents an organic group such as a hydrocarbon group, preferably methyl, ethyl, propyl, or phenyl. n represents 0, 1, or 2. R represents any of the functional groups shown in formulas (I-1) to (I-4) below.

[0176] CH2=C(R 3 )-COO-(CH2) p - (I-1)

[0177] CH2=C(R 4 )-C6H4- (I-2)

[0178] CH2=CH- (I-3)

[0179] HS-(CH2) p - (I-4)

[0180] Where R 3 and R 4 Each can be used to represent a hydrogen atom or a methyl group independently, and p represents an integer from 1 to 6.

[0181] Examples of functional groups represented by formula (I-1) include methacryloyloxyalkyl. Examples of siloxanes having this group include β-methacryloyloxyethyl dimethoxymethylsilane, γ-methacryloyloxypropyl methoxydimethylsilane, γ-methacryloyloxypropyl dimethoxymethylsilane, γ-methacryloyloxypropyl trimethoxysilane, γ-methacryloyloxypropyl ethoxydiethylsilane, γ-methacryloyloxypropyl diethoxymethylsilane, δ-methacryloyloxybutyl diethoxymethylsilane, etc.

[0182] As a functional group represented by formula (I-2), vinylphenyl can be cited as an example. Siloxanes having this group can be exemplified by vinylphenylethyldimethoxysilane.

[0183] Examples of siloxanes having the functional group shown in formula (I-3) include vinyltrimethoxysilane and vinyltriethoxysilane.

[0184] Mercaptoalkyl groups can be cited as functional groups represented by formula (I-4). Examples of siloxanes having this group include γ-mercaptopropyl dimethoxymethylsilane, γ-mercaptopropyl methoxydimethylsilane, γ-mercaptopropyl diethoxymethylsilane, γ-mercaptopropyl ethoxydimethylsilane, and γ-mercaptopropyl trimethoxysilane.

[0185] Siloxane cross-linking agents can be used alone or in combination of two or more.

[0186] As a siloxane crosslinking agent, 3-methacryloyloxypropylmethyldimethoxysilane is preferred because it is easy to form an island structure when polyorganosiloxane (A1) is compounded with vinyl polymer (A2).

[0187] The ratio of the siloxane-based cross-linking agent to 100% by mass of the organosiloxane mixture is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.5% by mass or more. On the other hand, it is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less. If the ratio of the siloxane-based grafting cross-linking agent is within the range of the above-mentioned upper and lower limits, covalent bonds between the polyorganosiloxane (A1) and the vinyl polymer (A2) can be sufficiently formed, and polymer particle clusters (C) with good impact strength can be obtained.

[0188] The ratio of the siloxane-based cross-linking agent to the organosiloxane mixture (100% by mass) can be, for example, 0.05–20% by mass, 0.1–10% by mass, or 0.5–5% by mass.

[0189] The number-average particle size of the polyorganosiloxane (A1) is preferably 1 nm or more, more preferably 10 nm or more, and even more preferably 30 nm or more. On the other hand, it is preferably 500 nm or less, more preferably 300 nm or less, more preferably 150 nm or less, particularly preferably 100 nm or less, particularly preferably 80 nm or less, and most preferably 60 nm or less. If the number-average particle size of the polyorganosiloxane (A1) is within the range of the above-mentioned upper and lower limits, it is easy to adjust the number-average particle size of the polymer particle group (C) to the range of the above-mentioned preferred upper and lower limits.

[0190] The number-average particle size of polyorganosiloxane (A1) can be, for example, 1–500 nm, 1–300 nm, 10–150 nm, 10–100 nm, 30–80 nm, or 30–60 nm.

[0191] The ratio of the mass average particle size (nm) to the number average particle size (nm) of the polyorganosiloxane (Al) (hereinafter also referred to as "Dw / Dn") is preferably 1.0 or higher, and on the other hand, preferably 1.7. If Dw / Dn is within the range of the above-mentioned upper and lower limits, the colorability of the resin composition containing the polymer particle group (C) and the thermoplastic resin is more excellent, and the color appearance of the molded article using the resin composition is more excellent.

[0192] The method for determining the number-average particle size (Dn) of polyorganosiloxane (A1) is the same as the method for determining the number-average particle size of polyorganosiloxane (A1) described above.

[0193] The method for determining the mass-average particle size (Dw) of polyorganosiloxane (A1) is the same as the method for determining the number-average particle size of polyorganosiloxane (A1) described above, except that the particle size distribution of the mass reference is used instead of the particle size distribution of the number reference. That is, the latex of polyorganosiloxane (A1) is diluted with deionized water to a concentration of about 3% as a sample, and the particle size distribution of the mass reference is determined using a capillary particle size analyzer (CHDF2000 particle size analyzer manufactured by MATEC Corporation, USA). The median diameter is taken as the mass-average particle size.

[0194] <Method for manufacturing polyorganosiloxane (A1)>

[0195] There are no particular limitations on the manufacturing method of polyorganosiloxane (A1), and the following manufacturing methods can be used for example.

[0196] First, an organosiloxane mixture containing organosiloxane, a desired siloxane-based crosslinking agent, a desired siloxane-based crosslinking agent, and a desired siloxane oligomer with end-capping groups is emulsified with an emulsifier and water to prepare an emulsion. In this emulsion, the organosiloxane mixture is polymerized at high temperature in the presence of an acid catalyst. Then, the acid catalyst is neutralized with an alkaline substance to obtain a method for manufacturing polyorganosiloxane latex.

[0197] In addition, the following description of the manufacturing method describes the case where a "mixture of organosiloxanes" is used as a raw material for polymerization, but the same manufacturing process can also be used when "organosiloxanes" are used.

[0198] In this manufacturing method, methods for preparing the emulsion include using a homogenizing mixer that atomizes particles using shear force from high-speed rotation, and a homogenizer that atomizes particles using the ejection force of a high-pressure generator, etc., which involve mixing by high-speed stirring. Among these, the method of using a homogenizer is preferred because it can narrow the particle size distribution of the polyorganosiloxane latex.

[0199] Examples of methods for mixing the acid catalyst during polymerization include (1) adding the organosiloxane mixture, emulsifier, and water along with the acid catalyst at one time for mixing; (2) adding an aqueous solution of the acid catalyst to an emulsion of the organosiloxane mixture at one time; and (3) adding the emulsion of the organosiloxane mixture dropwise to a hot aqueous solution of the acid catalyst at a certain rate for mixing. Among these methods, since the particle size of the polyorganosiloxane is easily controlled, the method of adding the emulsion of the organosiloxane mixture dropwise to a hot aqueous solution of the acid catalyst at a certain rate for mixing is preferred.

[0200] The polymerization temperature is preferably 50°C or higher, more preferably 70°C or higher. The upper limit of the polymerization temperature is, for example, 100°C.

[0201] When an emulsion of an organosiloxane mixture is added dropwise at a certain rate to a high-temperature aqueous solution of an acid catalyst for polymerization, the polymerization time is usually more than 2 hours, preferably more than 5 hours.

[0202] Furthermore, since cross-linking reactions between silanols occur at temperatures below 30°C, in order to increase the cross-linking density of polyorganosiloxanes, they can be polymerized at high temperatures above 50°C, and the resulting latex can be kept at temperatures below 30°C for approximately 5 to 100 hours.

[0203] In the polymerization reaction of organosiloxane mixtures, alkaline substances such as sodium hydroxide, potassium hydroxide, and ammonia solution can be used to neutralize the reaction system containing latex to a pH between 6 and 8, thereby terminating the polymerization reaction.

[0204] As for the emulsifier used in the above manufacturing method, there are no particular restrictions as long as it can emulsify the organosiloxane mixture, and anionic or nonionic emulsifiers are preferred.

[0205] Examples of anionic emulsifiers include sodium alkylbenzene sulfonate, sodium alkyl diphenyl ether disulfonate, sodium alkyl sulfate, sodium polyoxyethylene alkyl sulfate, and sodium polyoxyethylene nonylphenyl ether sulfate.

[0206] Examples of nonionic emulsifiers include: polyoxyethylene alkyl ethers, polyoxyethylene alkylene alkyl ethers, polyoxyethylene styrene phenyl ethers, polyoxyethylene tribenzyl phenyl ethers, and polyoxyethylene polyoxypropylene glycol.

[0207] These emulsifiers can be used alone or in combination of two or more.

[0208] The amount of emulsifier used relative to 100 parts by weight of the organosiloxane mixture is preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight or more, and preferably 20 parts by weight or less, more preferably 10 parts by weight or less. Depending on the amount of emulsifier used, the particle size of the polyorganosiloxane latex can be adjusted to a desired value. If the amount of emulsifier used is above the aforementioned lower limit, the emulsion stability of the organosiloxane mixture emulsion can be improved. When the amount of emulsifier used is below the aforementioned upper limit, the heat resistance and surface appearance of the molded article are superior.

[0209] Examples of acid catalysts for the polymerization of organosiloxane mixtures include sulfonic acids such as aliphatic sulfonic acids, aliphatic substituted benzenesulfonic acids, and aliphatic substituted naphthalenesulfonic acids, as well as inorganic acids such as sulfuric acid, hydrochloric acid, and nitric acid. These acid catalysts can be used individually or in combination of two or more. Among these, the use of inorganic acids such as sulfuric acid, hydrochloric acid, and nitric acid can narrow the particle size distribution of the polyorganosiloxane latex, further suppressing adverse effects caused by emulsifier components in the polyorganosiloxane latex (reduced heat resistance and poor appearance of the molded product).

[0210] The amount of acid catalyst used is preferably 0.005 parts by mass to 40 parts by mass relative to 100 parts by mass of organosiloxane. If the amount of acid catalyst used is 0.005 parts by mass or more, the organosiloxane mixture can be polymerized in a short time. If the amount of acid catalyst used is 40 parts by mass or less, the heat resistance and surface appearance of the molded article are better.

[0211] Furthermore, since the amount of acid catalyst used is a factor that determines the particle size of polyorganosiloxane (A1), in order to obtain polyorganosiloxane (A1) with the particle size described later, it is more preferable to use an amount of acid catalyst of 1 part by mass or more and 30 parts by mass relative to 100 parts by mass of organosiloxane.

[0212] To improve mechanical stability, an emulsifier can be added to the polyorganosiloxane latex obtained by the above method as needed. Preferably, the emulsifier is anionic or nonionic, as exemplified above.

[0213] (Vinyl Polymer (A2))

[0214] Vinyl polymers (A2) are polymers formed by the polymerization of vinyl monomer components (a2), and are composed of vinyl monomer-based units.

[0215] The vinyl monomer component (a2) constituting the vinyl polymer (A2) is composed of more than one vinyl monomer.

[0216] From the viewpoint of the impact strength of the molded article, the vinyl monomer component (a2) is preferably a monofunctional (meth)acrylate monomer (hereinafter also referred to as "monomer (a2-1)").

[0217] In addition to containing monomer (a2-1), the vinyl monomer component (a2) may also contain at least one of the following groups: monofunctional monomers (hereinafter also referred to as "monomer (a2-2)") that are different from monomer (a2-1) that can copolymerize with monomer (a2-1) and polyfunctional monomers (hereinafter also referred to as "monomer (a2-3)") that can copolymerize with monomer (a2-1).

[0218] From the viewpoint of the impact strength of the molded article and the viewpoint of setting the ratio of THF insoluble components in the polymer particle group (C) within the above range, the vinyl monomer component (a2) preferably contains monomer (a2-1) and monomer (a2-3).

[0219] Examples of monomers (a2-1) include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate; and alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, tridecyl methacrylate, and stearyl methacrylate.

[0220] From the perspective of improving the impact strength of the molded article, the monomer (a2-1) preferably contains at least one monomer selected from the group consisting of ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate and n-octyl acrylate, and more preferably contains n-butyl acrylate.

[0221] These monomers (a2-1) can be used alone or in combination of two or more.

[0222] Examples of monomers (a2-2) include aromatic vinyl monomers such as styrene and α-methylstyrene, cyanide vinyl monomers such as acrylonitrile and methacrylonitrile, and various vinyl monomers such as (meth)acryloyl-modified silicone. These monomers (a2-2) can be used alone or in combination of two or more.

[0223] Examples of monomers (a2-3) include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, divinylbenzene, polyfunctional (meth)acryloyl modified silicone, allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, and triallyl trimellitate.

[0224] Since the impact strength of the molded article is improved, the monomer (a2-3) is preferably selected from at least one of allyl methacrylate, triallyl cyanurate and triallyl isocyanurate, and more preferably allyl methacrylate.

[0225] These monomers (a2-3) can be used alone or in combination of two or more.

[0226] The ratio of monomer (a2-1) to vinyl monomer component (a2) in 100% by mass is preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass or more, from the viewpoint of the impact strength of the molded article.

[0227] The ratio of monomer (a2-1) to vinyl monomer component (a2) of 100% by mass can be 100% by mass, but is preferably 99.9% by mass or less.

[0228] From the viewpoint of the impact strength of the molded article, the ratio of monomer (a2-2) to vinyl monomer component (a2) of 100% by mass is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, particularly preferably 10% by mass or less, and may also be 0% by mass.

[0229] The ratio of monomer (a2-3) to vinyl monomer component (a2) in 100% by mass is preferably 0.1% by mass or more and 4% by mass or less.

[0230] From the viewpoint of further improving the impact strength of the molded article, the ratio of monomer (a2-3) to 100% by mass of vinyl monomer component (a2) is more preferably 0.1% by mass or more and 2% by mass or less, and even more preferably 0.1% by mass or more and 1% by mass or less.

[0231] From the viewpoint of further improving the color appearance of the molded article, the ratio of monomer (a2-3) to vinyl monomer component (a2) in 100% by mass is more preferably 0.5% by mass or more and 4% by mass or less, and even more preferably 1% by mass or more and 4% by mass or less.

[0232] From the viewpoint of melt flow during molding and the viewpoint of achieving a balance between the color appearance and impact strength of the molded body, the ratio of monomer (a2-3) to 100% by mass of vinyl monomer component (a2) is more preferably 0.3% by mass or more and 3% by mass or less, and even more preferably 0.5% by mass or more and 2.5% by mass or less.

[0233] (Polymer(A))

[0234] Polymer (A) comprises polyorganosiloxane (A1) and vinyl polymer (A2).

[0235] From the viewpoint of the impact strength of the molded article, the mass ratio of polyorganosiloxane (A1) to vinyl polymer (A2) in polymer (A) (hereinafter also referred to as "A1 / A2") is preferably 1 / 99 to 60 / 40, more preferably 1 / 99 to 40 / 60, and even more preferably 2 / 98 to 30 / 70.

[0236] <Method for manufacturing polymer (A)>

[0237] The manufacturing method of polymer (A) is not particularly limited, but from the perspective of better impact strength of the molded article, it is preferred to polymerize the vinyl monomer component (a2) that constitutes the vinyl polymer (A2) in the presence of a latex containing polyorganosiloxane (A1).

[0238] There are no particular limitations on the method of polymerizing the vinyl monomer component (a2) in the presence of a latex containing polyorganosiloxane (A1). Examples include (i) polymerizing the vinyl monomer component (a2) by dropwise addition to a latex containing polyorganosiloxane (A1); (ii) polymerizing the vinyl monomer component (a2) by adding a portion of the vinyl monomer component (a2) to a latex containing polyorganosiloxane (A1) without initiating polymerization, impregnating the polyorganosiloxane (A1) particles, initiating polymerization, and then adding or adding the remaining portion of the vinyl monomer component (a2) dropwise; and (iii) polymerizing the total amount of the vinyl monomer component (a2) by adding the latex containing polyorganosiloxane (A1) without initiating polymerization, impregnating the polyorganosiloxane (A1) particles, and then polymerizing.

[0239] As a method for manufacturing polymer (A), in the above-described manner, since the impact strength of the molded body is superior, it is preferable to add the total amount of the vinyl monomer component (a2) to a latex containing polyorganosiloxane (A1) without starting polymerization, and then polymerize the product after impregnating the polyorganosiloxane (A1) particles.

[0240] As a manufacturing method for polymer (A), a manufacturing method having the following steps i to iv is particularly preferred. According to this manufacturing method, a sea-island structure having polyorganosiloxane (A1) as the sea component and vinyl polymer (A2) as the island component, having multiple vinyl polymer (A2) regions in the polyorganosiloxane (A1) region, can easily obtain a polymer (A) that can achieve a polymer particle cluster (C) with a Z value of less than 60%.

[0241] Process i:

[0242] Latex of polyorganosiloxane (A1) is manufactured under any conditions.

[0243] The latex of polyorganosiloxane (A1) can be manufactured by the above method. In this case, the polyorganosiloxane (A1) is preferably composed of an organosiloxane and a siloxane-based crosslinking agent.

[0244] Process ii:

[0245] Under the condition that the vinyl monomer component (a2) has not started to polymerize, the total amount of the vinyl monomer component (a2) and the free radical polymerization initiator are added to the latex of the polyorganosiloxane (A1) obtained in step i, so that it is impregnated in the particles of polyorganosiloxane (A1).

[0246] At this point, by adding the full amount of the vinyl monomer component (a2), the impact strength of the molded part is even better.

[0247] When the vinyl monomer component (a2) contains multiple vinyl monomers, such as monomer (a2-1) and at least one monomer selected from the group consisting of monomer (a2-2) and monomer (a2-3), the method of adding these monomers is not particularly limited. For example, monomer (a2-1) and monomer (a2-2) and / or monomer (a2-3) may be added simultaneously, or monomer (a2-1) and monomer (a2-2) and / or monomer (a2-3) may be added separately.

[0248] When the vinyl monomer component (a2) contains monomer (a2-3), from the viewpoint of obtaining a suitable crosslinking structure, it is preferable to add it in combination with monomer (a2-1) and / or monomer (a2-2).

[0249] There are no particular limitations on what can be used as a free radical polymerization initiator; examples include azo compounds, peroxides, and dihalides. They can be used individually or in combination of two or more.

[0250] Examples of azo initiators include the following substances.

[0251] Oil-soluble azo initiators include 2,2'-azobisisobutyronitrile, dimethyl-2,2'-azobis(2-methylpropionate), 2,2'-azobis(2,4-dimethylpentanitrile), and 2,2'-azobis(2-butyronitrile); water-soluble azo initiators include 4,4'-azobis(4-cyanopentanoic acid), 2,2'-azobis[N-(2-carboxymethyl)-2-methylpropylamidine] hydrate, 2,2'-azobis-(N,N'-dimethyleneisobutylamidine) dihydrochloride, and 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride. These can be used individually or in combination of two or more.

[0252] When using an azo compound as a free radical polymerization initiator, the amount of azo compound used is preferably 0.01% by mass or more relative to 100% by mass of the total monomers to be polymerized, and more preferably 3% by mass or less, more preferably 1% by mass or less, and even more preferably 0.5% by mass or less. By keeping the amount of azo compound used within the upper and lower limits, excessive polymerization rate can be suppressed, and the island structure can be easily constructed.

[0253] Examples of peroxides include the following.

[0254] Inorganic peroxides such as hydrogen peroxide, potassium persulfate, and ammonium persulfate; and organic peroxides such as dicumyl peroxide, menthol peroxide, isocumyl peroxide, tert-butyl hydroperoxide, succinic acid peroxide, tert-butyl peroxyneodecanate, tert-butyl peroxyneoheptanoate, tert-butyl peroxyneoplastanoate, 1,1,3,3-tetramethylbutyl peroxide-2-ethylhexanoate, and tert-butyl peroxide-2-ethylhexanoate. These can be used individually or in combination of two or more. For ease of handling during emulsion polymerization, a 10-hour half-life temperature is preferably between 25°C and 105°C.

[0255] When using peroxide as a free radical polymerization initiator, the amount of peroxide used relative to 100% by mass of the total monomers to be polymerized is preferably 0.01% by mass or more, and more preferably 1% by mass or less, even more preferably 0.5% by mass or less, and still more preferably 0.2% by mass or less. By keeping the amount of peroxide used within the upper and lower limits, excessive polymerization rate can be suppressed, making it easier to construct the island structure.

[0256] Peroxides are preferred as free radical polymerization initiators because they allow for easy control of polymerization speed and result in superior impact strength of the molded product.

[0257] When using peroxides as free radical polymerization initiators, a reducing agent can be used in conjunction to promote the decomposition of the peroxides.

[0258] Examples of reducing agents include sulfur compounds such as sulfites, bisulfites, alkali metal bisulfites, acetone bisulfites, alkali metal sulfites, metabisulfites, and their salts; organosulfur compounds such as thiosulfates, sulfinic acids, hydroxyalkyl sulfinic acids, hydroxymethyl sulfinic acids, 2-hydroxy-2-sulfoacetic acid, formamidinic acid, propyl sulfinic acid, isopropyl sulfinic acid, and phenyl sulfinic acid; reducing nitrogen compounds such as formaldehyde hyposulfuric acid and its salts, hydroxylamine, hydroxylamine bisulfate, hydroxyammonium salts, polyamines, and dimethylaniline; reducing sugars such as sorbitol, fructose, glucose, lactose, and anhydrous glucose; and enediols such as ascorbic acid and isoascorbic acid. Examples of salts include sodium ions, potassium ions, ammonium ions, and zinc ions.

[0259] In addition, sulfates, nitrates, acetates, carbonates, and chlorides of transition metals located in Groups 3 to 11 of the periodic table can also be used as reducing agents. Examples of transition metals include Ce (Group 3), Ti (Group 4), V (Group 5), Cr and Mo (Group 6), Mn (Group 7), Fe (Group 8), Co (Group 9), Ni (Group 10), and Cu and Ag (Group 11).

[0260] As a reducing agent, based on its industrial availability and superior heat resistance, color change, and surface appearance of the molded article, at least one of the following groups is preferred: sodium formaldehyde sulfoxylate, L(+)-tartaric acid, sodium disulfite, sodium isoascorbate, L-ascorbic acid, and ferrous sulfate.

[0261] The amount of reducing agent used is preferably 2.0 molar equivalents or less of the peroxide used in the polymerization of the vinyl monomer component (a2), more preferably 1.0 molar equivalents or less, even more preferably 0.6 molar equivalents or less, and can also be 0 molar equivalents. By keeping the amount of reducing agent used below the aforementioned upper limit, excessive polymerization rate can be suppressed, and the island structure can be easily constructed.

[0262] When using transition metal salts as reducing agents, chelating agents can be used in conjunction to improve their reactivity.

[0263] As chelating agents, compounds containing two or more electron-donating atoms capable of forming coordinate bonds with the target transition metal atoms can be used. Examples include ethylenediaminetetraacetic acid (EDTA), hydroxyethylethylenediaminetriacetic acid (HEDTA), nitrotriacetic acid (NTA), citric acid, tartaric acid, gluconic acid, 5-sulfosalicylic acid, ethylenediamine, diethylenetriamine, triethylenetetraamine, triaminotriethylamine, triethanolamine, N-hydroxyethylethylenediamine, sodium oxalate, and their metal salts. Among these, EDTA and its metal salts are preferred due to their excellent polymerization stability.

[0264] From the perspective of controlling polymerization reactivity, the amount of chelating agent relative to the reducing agent is preferably 0.5 molar equivalents or more, more preferably 1.0 molar equivalents or more, and on the other hand, preferably 5.0 molar equivalents or less, more preferably 2.5 molar equivalents or less.

[0265] In step ii, an aqueous medium may be added to the latex of the polyorganosiloxane (A1) as needed.

[0266] Examples of aqueous media include water and mixtures of water and organic solvents. Any organic solvent in a mixture can be miscible with water; examples include methanol and ethanol.

[0267] In step ii, an emulsifier may be added to the latex of the polyorganosiloxane (A1) as needed.

[0268] There are no particular limitations on the emulsifier used; the same emulsifier used in the manufacture of the aforementioned polyorganosiloxane (A1) can be used. Anionic or nonionic emulsifiers are preferred.

[0269] Alternatively, in step ii, emulsifiers can be omitted, and polymerization can be carried out using only the emulsifiers contained in the polyorganosiloxane (A1) latex.

[0270] Chain transfer agents can be used when the vinyl monomer component (a2) is polymerized.

[0271] Examples of chain transfer agents include thiols such as n-dodecyl mercaptan, tert-dodecyl mercaptan, n-octyl mercaptan, n-tetradecyl mercaptan, n-hexyl mercaptan, and n-butyl mercaptan; halogen compounds such as carbon tetrachloride and ethylene bromide; and α-methylstyrene dimers. These chain transfer agents can be used individually or in combination of two or more.

[0272] The amount of chain transfer agent used is preferably 1.0% by mass or less relative to 100% by mass of the vinyl monomer component (a2), and can also be 0% by mass. By using the chain transfer agent at 1.0% by mass or less, the decrease in the proportion of THF insoluble components in the polymer particle group (C) can be suppressed, and the impact strength of the molded article is better.

[0273] Process iii:

[0274] For a latex of polyorganosiloxane (A1) in which vinyl monomer component (a2) and free radical polymerization initiator are added in step ii, the vinyl monomer component (a2) is polymerized under the condition that the following formula (a) is satisfied.

[0275] T 10 >(T in +10)···(a)

[0276] Here, T 10 T represents the 10-hour half-life temperature of the free radical polymerization initiator used. in This indicates the temperature at which the vinyl monomer component (a2) begins polymerization. When using multiple free radical polymerization initiators in combination, use the T value of the free radical polymerization initiator that indicates the minimum 10-hour half-life temperature. 10 value.

[0277] Satisfying equation (a), in other words, by the temperature T at which the vinyl monomer component (a2) begins polymerization. in (Hereinafter referred to as polymerization temperature (T)) in The temperature T is the 10-hour half-life temperature of the free radical polymerization initiator. 10Temperatures 10°C or lower can suppress polymerization rates, making it easier to construct the island-shaped composite of the aforementioned polyorganosiloxane (A1) and vinyl polymer (A2), resulting in polymer particle clusters (C) that enhance the impact strength of the molded body.

[0278] Polymerization temperature (T) in The preferred temperature is T, which is the 10-hour half-life temperature of the free radical polymerization initiator. 10 Temperatures 15°C or lower, more preferably 20°C or lower.

[0279] Polymerization temperature (T) in There is no particular limitation on the lower limit value of ), but from the viewpoint of stability at the start of polymerization, it is preferable to have a lower limit than the 10-hour half-life temperature T of the free radical polymerization initiator. 10 Lower than 50℃.

[0280] Polymerization time depends on polymerization temperature (T) in The duration varies, for example, from 0.1 to 30 hours.

[0281] 10-hour half-life temperature T 10 This refers to the temperature at which 50 mol% of the free radical polymerization initiator thermally decomposes within 10 hours. For example, by substituting the free radical polymerization initiator conversion rate X = 50% [%, time t = 36000 [s] (= 10 hours), gas constant R = 8.314 [J / Kmol], frequency factor A, and activation energy E into the following equations (b) and (c), using literature values ​​or calculated values, the 10-hour half-life temperature T of the free radical polymerization initiator can be calculated. 10 The temperature T, representing the 10-hour half-life. 10 Alternatively, literature values ​​can be used.

[0282] X = 100 × exp(-kdt)···(b)

[0283] kd=A×exp(-E / RT)···(c)

[0284] (X[%]: Conversion rate, kd[1 / S]: Reaction rate, t[s]: Time, A[1 / S]: Frequency factor, E[J / mol]: Activation energy, R[J / Kmol]: Gas constant, T[K]: Temperature)

[0285] For example, potassium persulfate has a 10-hour half-life temperature of 67°C, and tert-butyl hydroperoxide (trade name PERBUTYLH69, manufactured by Nippon Oils & Fats Co., Ltd.) has a 10-hour half-life temperature of 167°C.

[0286] Process iv:

[0287] In step iii, during the polymerization behavior after the polymerization begins, the highest temperature reached within the system by the polymerization of the vinyl monomer component (a2) is set as Tp (°C), and the temperature within the system reaches T... in +1 (°C) after reaching T in +{(T p -T in The time required to calculate 3°C is set to S. p (seconds) (hereinafter referred to as polymerization rate (S) p When ), aggregation is performed in a manner that satisfies the following formula (d).

[0288] S p ≥80···(d)

[0289] By increasing the polymerization rate (S) p With a polymerization time of 80 seconds or more, it is easy to construct the island-shaped composite structure of the aforementioned polyorganosiloxane (A1) and vinyl polymer (A2), which can yield polymer particle clusters (C) that result in molded articles with better impact strength. Polymerization rate (S) p More preferably, it is 100 seconds or more, even more preferably 120 seconds or more, and particularly preferably 150 seconds or more.

[0290] Polymerization rate (S) p In addition to the above-mentioned types and amounts of free radical polymerization initiators and polymerization start temperature T, in In addition, adjustments can be made through a slow heating system during polymerization.

[0291] (Vinyl Polymer (B))

[0292] Vinyl polymer (B) is a polymer formed by polymerizing vinyl monomer component (b), and is composed of vinyl monomer-based units.

[0293] The vinyl monomer component (b) constituting the vinyl polymer (B) is composed of more than one vinyl monomer.

[0294] The vinyl monomers constituting vinyl monomer component (b) are not particularly limited, and various vinyl monomers such as (meth)acrylate monomers, aromatic vinyl monomers, and cyanide vinyl monomers can be cited as examples.

[0295] Examples of (meth)acrylate monomers include alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and isobutyl methacrylate; and alkyl acrylates such as methyl acrylate, ethyl acrylate, and n-butyl acrylate.

[0296] Examples of aromatic vinyl monomers include styrene, alkyl-substituted styrene (p-methylstyrene, m-methylstyrene, o-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, p-ethylstyrene, m-ethylstyrene, o-ethylstyrene, etc.), alkyl-substituted isopropylbenzenes (isopropylbenzene (α-methylstyrene), isopropyltoluene, isopropylbenzene ... octylbenzene, etc.), and 1,1-diphenylethylene. Among these, styrene and α-methylstyrene are preferred from the perspective of suppressing fragmentation.

[0297] Examples of vinyl cyanide monomers include acrylonitrile and methacrylonitrile.

[0298] They can be used individually or in combination of two or more.

[0299] From the viewpoint of superior weather resistance of the molded article, the vinyl monomer component (b) preferably contains at least one selected from the group consisting of (meth)acrylate monomers and aromatic vinyl monomers.

[0300] The ratio of (meth)acrylate monomers and aromatic vinyl monomers to 100% by mass of vinyl monomer component (b) is preferably 50% by mass or more.

[0301] The vinyl monomer component (b) is preferably composed of either or both of methyl methacrylate and styrene, based on the perspective of the particularly excellent weather resistance of the molded article.

[0302] The ratio of methyl methacrylate and styrene to 100% by mass of vinyl monomer component (b) is preferably 50% by mass or more.

[0303] From the perspective of better dispersibility of polymer particle groups (C) in thermoplastic resin and better weather resistance of molded articles, the vinyl monomer component (b) preferably contains (meth)acrylate monomers.

[0304] The ratio of (meth)acrylate monomer to vinyl monomer component (b) 100% by mass is preferably 50% by mass or more.

[0305] The vinyl monomer component (b) in the (meth)acrylate monomer is more preferably methyl methacrylate, based on the particularly excellent dispersibility of the polymer particle group (C) in the thermoplastic resin and the weather resistance of the molded article.

[0306] The ratio of methyl methacrylate to 100% by mass of vinyl monomer component (b) is more preferably 50% by mass or more.

[0307] The glass transition temperature (hereinafter also referred to as "Tg") of the vinyl polymer (B) is preferably 70°C or higher, more preferably 80°C or higher, even more preferably 90°C or higher, and on the other hand, preferably 105°C or lower. If the Tg of the vinyl polymer (B) is above the lower limit mentioned above, the powder properties (powder flowability or particle size) of the polymer particle group (C) are good.

[0308] The Tg of the vinyl polymer (B) can be adjusted according to the type and ratio of the vinyl monomers that make up the vinyl monomer component (b).

[0309] The Tg of the vinyl polymer (B) is obtained using the FOX formula. In this case, the Tg of the homopolymer of the vinyl monomers constituting the vinyl monomer component (b) can be, for example, used the values ​​described in the "Polymer Handbook" (Wiley Interscience / 1999). The Tg of vinyl monomer homopolymers not described in that literature can be calculated using the Bicerano method "Prediction of Polymer Properties" (MARCEL DEKKER / 2002).

[0310] (Method for manufacturing polymer particle swarms (C))

[0311] The polymer particle group (C) can be manufactured, for example, by polymerizing the vinyl monomer component (b) in the presence of polymer (A) (graft polymerization). This yields a polymer on which some or all of the vinyl polymer (B) has been grafted.

[0312] As a method for manufacturing polymer particle clusters (C), it is preferable to add vinyl monomer component (b) to the latex of polymer (A) and polymerize vinyl monomer component (b) in the latex.

[0313] As described above, the latex of polymer (A) is preferably manufactured by polymerizing the vinyl monomer component (a2) in the presence of a latex containing polyorganosiloxane (A1).

[0314] The temperature at which the vinyl monomer component (b) is polymerized (hereinafter referred to as the "polymerization temperature (T)") b There are no special restrictions; conventional conditions can be applied, such as 45–95°C and polymerization time of 0.1–10 hours.

[0315] The method for adding vinyl monomer component (b) to the latex of polymer (A) is not particularly limited, but dropwise addition is preferred from the perspective of suppressing the generation of debris and achieving a good grafting rate between polymer (A) and vinyl monomer component (b). At this time, the total amount of vinyl monomer component (b) can be added dropwise continuously, or it can be added dropwise in multiple times by setting a holding time during which vinyl monomer component (b) is not added dropwise.

[0316] When the vinyl monomer component (b) is composed of multiple vinyl monomers, there is no particular limitation on the method for continuously adding the total amount of vinyl monomer component (b). Examples include continuously adding a mixture of the same composition, or adding it while continuously changing the composition, as in mechanically fed polymerization. When the vinyl monomer component (b) is composed of multiple vinyl monomers, as a method of adding it dropwise in multiple stages with a holding time in between, examples include adding a mixture of the same composition in multiple stages, or adding each component monomer and / or a mixture of different compositions in multiple stages.

[0317] When the vinyl monomer component (b) contains (meth)acrylate monomer, aromatic vinyl monomer, and cyanide vinyl monomer, it is preferable to polymerize the (meth)acrylate monomer, followed by polymerizing the aromatic vinyl monomer and the cyanide vinyl monomer. The polymer particle group (C) obtained by polymerization using this method, followed by a powder recovery process, exhibits good powder properties (powder flowability or particle size).

[0318] The vinyl monomer component (b) can form a graft polymer with polymer (A) by chemically bonding with units of siloxane-based crosslinkers contained in polyorganosiloxane (A1) and / or units of monomers (a2-3) contained in vinyl polymer (A2).

[0319] To improve the efficiency of this grafting, before adding the vinyl monomer component (b), for example, multifunctional monomers such as ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, divinylbenzene, polyfunctional (meth)acryloyl-modified silicone, allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, and triallyl trimellitate can be prepolymerized.

[0320] There are no particular restrictions on the emulsifier used when polymerizing the vinyl monomer component (b). The same emulsifier used in the manufacture of the polyorganosiloxane (A1) and / or the vinyl polymer (A2) can be used, but anionic or nonionic emulsifiers are preferred. Furthermore, no special emulsifier is added during the polymerization of the vinyl monomer component (b), and polymerization is carried out using only the emulsifier contained in the vinyl polymer (A2) latex.

[0321] The total amount of emulsifier used in the manufacture of polysiloxane (A1), the manufacture of vinyl polymer (A2), and the polymerization of vinyl monomer component (b) is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and preferably 10 parts by mass or less, more preferably 5 parts by mass or less, relative to 100 parts by mass of all monomers forming polymer particle cluster (C). Depending on the total amount of emulsifier, the particle size of the polymer particle cluster (C) latex can be adjusted to a desired value. If the total amount of emulsifier is above the aforementioned lower limit, the stability of each of the polysiloxane (A1) latex, polymer (A) latex, and polymer (C) latex can be sufficiently improved. If the total amount of emulsifier is below the aforementioned upper limit, the amount of residual emulsifier in the polymer particle cluster (C) powder can be sufficiently reduced, and the reduction in the heat resistance and surface appearance of the molded article using the resin composition containing polymer particle cluster (C) and thermoplastic resin can be suppressed.

[0322] Chain transfer agents can also be used to adjust the THF-soluble components and molecular weight when polymerizing vinyl monomer components (b).

[0323] Examples of chain transfer agents include thiols such as n-dodecyl mercaptan, tert-dodecyl mercaptan, n-octyl mercaptan, n-tetradecyl mercaptan, n-hexyl mercaptan, and n-butyl mercaptan; halogen compounds such as carbon tetrachloride and ethylene bromide; and α-methylstyrene dimers. These chain transfer agents can be used individually or in combination of two or more.

[0324] The amount of chain transfer agent used is preferably 2.0% by mass or less relative to 100% by mass of the vinyl monomer component (b), and can also be 0% by mass. By making the amount of chain transfer agent used 2.0% by mass or less, the reduction in the ratio of THF-insoluble components of the polymer particle group (C) is suppressed, and the impact strength of the molded article is better.

[0325] Alternatively, after polymerizing the vinyl monomer component (b), the polymer particle group (C) can be recovered as powder from the latex of the resulting polymer particle group (C).

[0326] When recovering polymer particle clusters (C) as powder, direct drying methods such as spray drying or flocculation methods can be used. In the flocculation method, the washing process after flocculation can reduce the residues of polymerization aids such as emulsifiers, flocculants, and initiators used during polymerization in the resulting powder. On the other hand, in the direct drying method, the additives added during polymerization can remain largely in the resulting powder. When adding polymer particle clusters (C) to thermoplastic resins, these powder recovery methods can be appropriately selected to achieve a preferred residue state.

[0327] Spray drying is a method in which polymer particle cluster (C) latex is sprayed into a dryer as tiny droplets, and dried by contact with a heating gas. Examples of methods for generating tiny droplets include rotating disc type, pressure nozzle type, two-fluid nozzle type, and pressurized two-fluid nozzle type. The capacity of the dryer can range from small-scale laboratory use to large-scale industrial use. The temperature of the heating gas is preferably below 200°C, more preferably 120–180°C. Latexes of two or more graft copolymers prepared separately can also be spray-dried together. Furthermore, to improve powder properties such as adhesion and bulk density during spray drying, any component such as silica can be added to the polymer particle cluster (C) latex for spray drying.

[0328] The coagulation method involves flocculating polymer particle clusters (C) latex, separating, recovering, and drying the polymer particle clusters (C). First, polymer (C) latex is added to hot water containing a coagulant, causing salting out and coagulation, thereby separating the polymer particle clusters (C). Next, the separated, wet polymer particle clusters (C) are dehydrated to recover the polymer particle clusters (C) with reduced moisture content. The recovered polymer particle clusters (C) are then dried using a press dehydrator or a hot air dryer.

[0329] Examples of coagulants include inorganic salts such as aluminum chloride, aluminum sulfate, sodium sulfate, magnesium sulfate, sodium nitrate, and calcium acetate; acids such as sulfuric acid; and calcium acetate is particularly preferred. These coagulants can be used alone or in combination of two or more.

[0330] The aforementioned coagulant is typically used as an aqueous solution. From the viewpoint of stably coagulating and recovering the polymer particle clusters (C), the concentration of the coagulant aqueous solution is preferably 0.1% by mass or more, and particularly preferably 1% by mass or more. Furthermore, from the viewpoint of reducing the amount of coagulant remaining in the recovered polymer particle clusters (C) to prevent a decrease in the molded appearance of the molded article, the concentration of the coagulant aqueous solution is preferably 20% by mass or less, and particularly preferably 15% by mass or less.

[0331] The amount of coagulant aqueous solution is not particularly limited, but it is preferably 10 parts by mass or more and 500 parts by mass relative to 100 parts by mass of polymer particle group (C) latex.

[0332] There are no particular limitations on the method of contacting the polymer particle cluster (C) latex with the coagulant aqueous solution; the following methods are generally applicable.

[0333] (1) A method of continuously adding latex to an aqueous coagulant solution while stirring it and maintaining the solution for a certain period of time.

[0334] (2) A method of continuously injecting a coagulant aqueous solution and latex in a certain proportion into a container equipped with a mixer and bringing them into contact, and continuously extracting a mixture of flocculated polymer and water from the container.

[0335] There is no particular limitation on the temperature at which the latex comes into contact with the coagulant aqueous solution, but it is preferably above 30°C and below 100°C. There is no particular limitation on the contact time.

[0336] The flocculated polymer particle clusters (C) are washed with approximately 1 to 100 times their mass of water and then filtered. The filtered, moist polymer particle clusters (C) are then dried using a flow dryer or a press dehydrator. The drying temperature and time can be appropriately determined based on the obtained polymer particle clusters (C).

[0337] Alternatively, the polymer particle clusters (C) discharged from the press dehydrator or extruder can be sent directly to the extruder or molding machine used to manufacture the resin composition without being recycled, and mixed with thermoplastic resin to obtain the molded article.

[0338] [Composition]

[0339] One embodiment of the present invention relates to a composition (hereinafter also referred to as "the composition") comprising at least one component (hereinafter also referred to as "component (D)") selected from the group consisting of polymer particle groups (C), phosphoric acid compounds and their alkali metal salts.

[0340] Component (D) plasticizes the resin composition containing polymer particle clusters (C), improving the flowability of the resin composition during formation. Furthermore, it can suppress the decrease in the molecular weight of the resin composition and improve molding stability.

[0341] Examples of phosphoric acid compounds in component (D) include alkyl phosphoric acids such as polyoxyalkylene alkyl ether phosphoric acid and alkylaryl phosphoric acid such as polyoxyalkylene alkylphenyl ether phosphoric acid.

[0342] In polyoxyalkylene phenyl ether phosphoric acid and polyoxyalkylene alkyl ether phosphoric acid, polyoxyethylene and the like can be cited as polyoxyalkylene groups, with polyoxyethylene being preferred. The number of oxyethylene units in the polyoxyethylene group is, for example, 2 to 14, preferably 2 to 10, more preferably 2 to 8, and even more preferably 2 to 6. The number of carbon atoms in the alkyl group is, for example, 1 to 20, preferably 5 to 18, more preferably 7 to 16, and even more preferably 10 to 16.

[0343] Examples of alkali metal salts include sodium salts and potassium salts.

[0344] As component (D), from the viewpoint of easily adjusting the phosphorus atom content (described later), alkali metal salts of phosphoric acid compounds are preferred, and alkali metal salts of alkyl phosphoric acid and alkylaryl phosphoric acid are more preferred. From the viewpoint of the flowability and molding stability of the resin composition during molding, alkali metal salts of polyoxyethylene alkylphenyl ether phosphoric acid and polyoxyethylene alkyl ether phosphoric acid are preferred, and alkali metal salts of polyoxyethylene alkyl ether phosphoric acid are more preferred.

[0345] As an alkali metal salt of polyoxyethylene alkylphenyl ether phosphoric acid, an alkali metal salt of polyoxyethylene alkylphenyl ether phosphoric acid is preferred.

[0346] Alkali metal salts of polyoxyethylene alkyl ether phosphoric acid are preferred.

[0347] Among them, alkali metal salts of polyoxyethylene alkyl ether phosphoric acid are preferred.

[0348] These compounds can be used alone or in combination of two or more.

[0349] The content of component (D) in this composition is set with reference to the ratio of phosphorus atoms contained in component (D) relative to the total mass of polymer particle group (C) and component (D) (hereinafter also referred to as "phosphorus content").

[0350] From the viewpoint of the flowability and molding stability of the resin composition during molding, the phosphorus content is preferably 10 ppm by mass or more, more preferably 50 ppm by mass or more, further preferably 100 ppm by mass or more, particularly preferably 200 ppm by mass or more, and most preferably 300 ppm by mass or more. There is no particular upper limit to the phosphorus atom content; for example, it is 2000 ppm by mass or less, preferably 1500 ppm by mass or less.

[0351] The composition may further include other emulsifiers besides component (D). There are no particular limitations on other emulsifiers; for example, the same emulsifier used in the manufacture of the polymer particle group (C) may be used.

[0352] The total ratio of polymer particle group (C) and component (D) relative to 100% by mass of the composition is preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 98% by mass or more.

[0353] A preferred embodiment of this composition is the recovery of powder from a latex comprising a polymer particle group (C) and an emulsifier, wherein at least a portion of the emulsifier is an alkali metal salt of the phosphate compound.

[0354] The composition can be manufactured, for example, by adding an alkali metal salt of a phosphoric acid compound to the polymer particle group (C) latex (which may also contain other emulsifiers) for powder recovery, or by adding an alkali metal salt of a phosphoric acid compound during the polymerization process of the polymer particle group (C) (during the polymerization of polymer (A) or vinyl polymer (B)) and recovering the powder. As a powder recovery method, the same method as the method for recovering the polymer particle group (C) in powder form from the aforementioned polymer particle group (C) latex can be cited.

[0355] However, this composition is not limited to this. For example, it may also be a substance formed by mixing polymer particle clusters (C) powder and component (D).

[0356] [Resin Composition]

[0357] A resin composition of one aspect of the present invention (hereinafter also referred to as "the resin composition") comprises a group of polymer particles (C) and a thermoplastic resin (hereinafter also referred to as "the thermoplastic resin (E)").

[0358] The resin composition of the present invention may contain a component that replaces the polymer particle group (C). In this case, the resin composition contains the polymer particle group (C), component (D), and thermoplastic resin (E).

[0359] Thermoplastic resin (E) is not particularly limited, and examples include engineering plastics (aromatic polycarbonate, etc.), styrene resins, polyester resins, olefin resins (polyethylene, etc.), thermoplastic elastomers, biodegradable resins, halogen resins (vinyl chloride resin, etc.), acrylic resins, etc.

[0360] As an engineering plastic, various well-known thermoplastic engineering plastics can be used without particular restrictions.

[0361] Examples of engineering plastics include polyphenylene ether, polycarbonate, polyester polymers (polyethylene terephthalate, polybutylene terephthalate, etc.), syndiotactic polystyrene, nylon polymers (6-nylon, 6,6-nylon, etc.), polyarylate, polyphenylene sulfide, polyetherketone, polyetheretherketone, polysulfone, polyamide-imide, polyetherimide, and polyacetal.

[0362] In addition, special styrene-based resins such as heat-resistant ABS, which have excellent heat resistance and require melt flowability, or heat-resistant acrylic resins, can also be used as engineering plastics in this invention. Among them, aromatic polycarbonate or polybutylene terephthalate are more preferred when strength performance is required.

[0363] Examples of aromatic polycarbonates include 4,4'-dioxydiaryl alkane polycarbonates such as 4,4'-dihydroxydiphenyl-2,2-propane (i.e., bisphenol A) polycarbonates.

[0364] Examples of olefin-based resins include high-density polyethylene, medium-density polyethylene, low-density polyethylene, copolymers of ethylene and other α-olefins; copolymers of polypropylene, propylene and other α-olefins; polybutene, poly-4-methyl-1-pentene, etc.

[0365] Examples of thermoplastic elastomers include styrene-based elastomers, polyurethane-based elastomers, polyolefin-based elastomers, polyamide-based elastomers, fluorinated elastomers, chlorinated PE-based elastomers, and acrylic elastomers.

[0366] Examples of styrene-based elastomers include styrene-butadiene-styrene copolymer (SBS), styrene-isoprene-styrene copolymer (SIS), styrene-ethylene-butene copolymer (SEB), styrene-ethylene-propylene copolymer (SEP), styrene-ethylene-butene-styrene copolymer (SEBS), styrene-ethylene-propylene-styrene copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene copolymer (SEEPS), styrene-butadiene-butene-styrene copolymer (partially hydrogenated styrene-butadiene-styrene copolymer: SBBS), partially hydrogenated styrene-isoprene-styrene copolymer, and partially hydrogenated styrene-isoprene-butadiene-styrene copolymer. "-" indicates copolymerization of monomers forming units connected by "-", while "·" indicates copolymerization followed by random modification such as hydrogenation.

[0367] Examples of polyurethane elastomers include the reaction products of high molecular weight diols with organic diisocyanates and chain extenders.

[0368] Examples of high molecular weight diols include polyester diol, polyether diol, polyester ether diol, polycarbonate diol, and polyester polycarbonate diol.

[0369] Examples of organic diisocyanates include 4,4'-diphenylmethane diisocyanate, toluene diisocyanate, terephthalic diisocyanate, phenyl dimethyl diisocyanate, naphthalene diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate (4,4'-dicyclohexylmethane diisocyanate), isophorone diisocyanate, and hexamethylene diisocyanate. Among these organic diisocyanates, 4,4'-diphenylmethane diisocyanate is preferred.

[0370] Examples of chain extenders include ethylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 2-methyl-1,3-propanediol, 1,6-hexanediol, neopentanediol, 1,9-nonanediol, cyclohexanediol, and 1,4-bis(β-hydroxyethoxy)benzene.

[0371] Examples of polyolefin-based elastomers include ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-vinyl acetate copolymer, butyl rubber, butadiene rubber, propylene-butene copolymer, and ethylene-acrylate copolymer.

[0372] Examples of styrene-based resins include polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-styrene-α-methylstyrene copolymer, acrylonitrile-methyl methacrylate-styrene-α-methylstyrene copolymer, ABS resin, AS resin, MABS resin, MBS resin, AAS resin, AES resin, acrylonitrile-butadiene-styrene-α-methylstyrene copolymer, acrylonitrile-methyl methacrylate-butadiene-styrene-α-methylstyrene copolymer, styrene-maleic anhydride copolymer, styrene-maleimide copolymer, styrene-N-substituted maleimide copolymer, acrylonitrile-styrene-N-substituted maleimide copolymer, acrylonitrile-butadiene-styrene-β-isopropenylnaphthalene copolymer, and acrylonitrile-methyl methacrylate-butadiene-styrene-α-methylstyrene-maleimide copolymer, etc.

[0373] Polyester resins are polymers of polybasic acids and polyols, with no particular limitation on their thermoplasticity. Examples of polybasic acids include terephthalic acid, naphthalene dicarboxylic acid, cyclohexyl dicarboxylic acid and its esters. Polyols include ethylene glycol, propylene glycol, butanediol, pentanediol, neopentanediol, hexanediol, octanediol, decanediol, cyclohexanediol, hydroquinone, bisphenol A, 2,2-bis(4-hydroxyethoxyphenyl)propane, 1,4-dimethyloltetrabromobenzene, tetrabromobisphenol A bis(2-hydroxyethyl) ether (TBA-EO), etc.

[0374] Polyester resins can be homopolymers, copolymers, or mixtures of two or more of these.

[0375] As a polyester resin, commercially available products such as "PETG" manufactured by Eastman Chemical Co., Ltd. can also be used.

[0376] Examples of biodegradable resins include microbial polymers, chemically synthesized dead polymers, and natural polymers.

[0377] Examples of microbial polymers include biopolyesters such as polyhydroxybutyrate / valerate (PHB / V), bacterial cellulose, and microbial polysaccharides (pullulan, curdlan, etc.).

[0378] Examples of chemically synthesized polymers include aliphatic polyesters (polycaprolactone, polybutylene succinate, polyethylene succinate, polyglycolic acid, polylactic acid, etc.), polyvinyl alcohol, and polyamino acids (PMLG, etc.).

[0379] Examples of natural polymers include chitosan, cellulose, starch, and cellulose acetate.

[0380] Examples of halogenated resins include vinyl chloride homopolymers, copolymers containing vinyl chloride in a proportion of 80% or more by mass, and highly chlorinated polyvinyl chloride resins. In addition to vinyl chloride, examples of copolymer components include monoethylene compounds such as ethylene, vinyl acetate, methyl methacrylate, and butyl acrylate. These compounds may be present in the copolymer in a proportion of 20% or less by mass.

[0381] Besides vinyl chloride resin, other halogenated resins include fluorinated polymers, brominated polymers, and iodinated polymers.

[0382] Examples of acrylic resins include copolymers formed by polymerizing methyl methacrylate with copolymerizable vinyl monomers. Examples of copolymerizable vinyl monomers include alkyl acrylates such as methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate; alkyl methacrylates such as ethyl methacrylate, propyl methacrylate, and n-butyl methacrylate; and aromatic vinyl compounds such as styrene, α-methylstyrene, and methylstyrene.

[0383] Polyester resins such as polyphenylene ether, polycarbonate, polyethylene terephthalate and polybutylene terephthalate, polyamide resins such as syndiotactic polystyrene, 6-nylon and 6,6-nylon, polymer alloys of engineering plastics such as polyarylate, polyphenylene sulfide, polyetherketone, polyetheretherketone, polysulfone, polyethersulfone, polyamide imide, polyetherimide, polyacetal and other thermoplastic resins are also included in the scope of the thermoplastic resins (E) of this invention.

[0384] These thermoplastic resins (E) can be used alone or in combination of two or more.

[0385] Based on the consideration of easy availability in industry and an excellent balance between impact strength and colorability of the molded article, the thermoplastic resin (E) preferably contains at least one selected from the group consisting of aromatic polycarbonate, polymethyl methacrylate, styrene-acrylonitrile copolymer, polyethylene terephthalate, polybutylene terephthalate, polyvinyl chloride, polyphenylene sulfide and polyacetal, and more preferably contains at least one selected from the group consisting of polymethyl methacrylate and styrene-acrylonitrile copolymer.

[0386] In addition to the above, the resin composition of the present invention may also contain various known additives without prejudice to the purpose of the present invention.

[0387] Examples of additives include flame retardants (phosphorus-based, bromine-based, silicone-based, organometallic salt-based, etc.), anti-drip agents (e.g., fluorinated polyolefins, silicones, and aromatic polyamide fibers), lubricants (e.g., long-chain fatty acid metal salts such as magnesium stearate), mold release agents (e.g., pentaerythritol tetrastearate), nucleating agents, antistatic agents, stabilizers (e.g., phenolic stabilizers, sulfur-based stabilizers, phosphorus stabilizers, UV absorbers, amine light stabilizers, etc.), fillers (titanium oxide, talc, mica, kaolin, calcium carbonate, glass sheets, etc.), plasticizers, reinforcing agents (e.g., glass fiber, carbon fiber, etc.), pigments, and colorants.

[0388] Phenolic stabilizers are stabilizers containing phenolic hydroxyl groups. Preferably, hindered phenolic antioxidants are used where one or two carbon atoms adjacent to the carbon atom of the aromatic ring bound to the phenolic hydroxyl group are substituted with substituents having four or more carbon atoms. In this case, the substituents having four or more carbon atoms can bind to the carbon atoms of the aromatic ring via carbon-carbon bonds, or they can bind through atoms other than carbon atoms.

[0389] Examples of phenolic stabilizers include unhindered phenolic antioxidants such as p-cyclohexylphenol, 3-tert-butyl-4-methoxyphenol, 4,4'-isopropylidene diphenol, and 1,1-bis(4-hydroxyphenyl)cyclohexane; 2-tert-butyl-4-methoxyphenol; 2,6-di-tert-butyl-p-cresol; 2,4,6-tri-tert-butylphenol; 4-hydroxymethyl-2,6-di-tert-butylphenol; styrylated phenol; 2,5-di-tert-butylhydroquinone; and octadecyl-3-(3, 5-Di-tert-butyl-4-hydroxyphenyl)propionate, triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythritol tetraphilic[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2 2,2'-Methylenebis[4-methyl-6-(1,3,5-trimethylhexyl)phenol], 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), 2,6-bis(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methylphenol, 1,1,3-tris[2-methyl-4-hydroxy-5-tert-butylphenyl]butane, 1,3,5-trimethyl-2,4,6-tris[3, Hindered phenolic antioxidants include [5-di-tert-butyl-4-hydroxybenzyl]benzene, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, tris[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propoxyethyl]isocyanurate, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-thiobis(4-methyl-6-tert-butylphenol), 4,4'-thiobis(2-methyl-6-tert-butylphenol), and thiobis(β-naphthol). Hindered phenolic antioxidants, in particular, are suitable for use as free radical scavengers because they readily become stable free radicals themselves. These phenolic stabilizers can be used alone or in combination of two or more.

[0390] Relative to 100% by mass of the resin composition, the content of the phenolic stabilizer is preferably 0.001% by mass or more, more preferably 0.003% by mass or more, and preferably 2% by mass or less, more preferably 1% by mass or less. If the content of the phenolic stabilizer is at or above the lower limit mentioned above, the antioxidant effect is excellent; if it is at or below the upper limit mentioned above, the oxidative thermal stability of the resin composition and the resin decomposition during melt mixing can be further suppressed.

[0391] Sulfur-based stabilizers are stabilizers containing sulfur atoms but not phenolic hydroxyl groups. They function as decomposers of hydroperoxides produced during the degradation of thermoplastic resins, thus improving the heat aging resistance of resin compositions and enhancing the retention of color, tensile strength, and elongation. Sulfur-based stabilizers can be used alone, but when used in combination with the aforementioned phenolic stabilizers, long-term thermal stability can be further improved.

[0392] Examples of sulfur-based stabilizers include, for instance, didodecyl thiodipropionate, ditetradecyl thiodipropionate, dioctadecyl thiodipropionate, pentaerythritol tetra(3-dodecyl thiopropionate), thiobis(N-phenyl-β-naphthylamine), 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, nickel dibutyldithiocarbamate, nickel isopropyl xanthate, and trilauryl trithiophosphite. In particular, sulfur-ether stabilizers with a sulfur-ether structure can be appropriately used for the reduction of oxidized substances by accepting oxygen. These sulfur-based stabilizers can be used alone or in combination of two or more.

[0393] Relative to 100% by mass of the resin composition, the content of the sulfur-based stabilizer is preferably 0.001% by mass or more, more preferably 0.003% by mass or more, and preferably 2% by mass or less, more preferably 1% by mass or less. If the content of the sulfur-based stabilizer is at or above the lower limit mentioned above, the heat stabilization effect is excellent; if it is at or below the upper limit mentioned above, the resin decomposition during melt mixing of the resin composition can be further suppressed.

[0394] Phosphorus-based stabilizers are stabilizers containing phosphorus atoms and are phosphite compounds with a P(OR)3 structure. Here, R can be alkyl, alkylene, aryl, aryl, etc., and the three Rs can be the same or different; two Rs can form a ring structure. Furthermore, a molecule can have multiple P(OR)3 structures. Phosphorus-based stabilizers function as decomposers of hydroperoxides generated during the deterioration of thermoplastic resins, thus improving the heat aging resistance of resin compositions and enhancing the retention of color, tensile strength, and elongation. Phosphorus-based stabilizers can be used alone, but when used in combination with phenolic stabilizers, they particularly improve long-term thermal stability and suppress yellowing caused by phenolic stabilizers.

[0395] Examples of phosphite compounds include triaryl phosphites (triphenyl phosphite, trimethyl phosphite, tri(dimethyl) phosphite, trinaphthyl phosphite, etc.), diarylalkyl phosphites (diphenyl isooctyl phosphite, diphenyl decyl phosphite, etc., diaryl C1-18 alkyl phosphites, etc.), aryl dialkyl phosphites (phenyl diisooctyl phosphite, etc., aryl C1-18 dialkyl phosphites, etc.), and trialkyl phosphites (trimethyl phosphite, etc.). Triethyl phosphite, tri-n-butyl phosphite, triisooctyl phosphite, tridecanyl phosphite, triisodecyl phosphite, etc. (triC1-18 alkyl phosphites, etc.), dialkyl phosphites (dilauryl phosphite, etc. (diC1-18 alkyl phosphites, etc.), phosphites containing alkyl aryl units [tris(2,4-tert-butylphenyl) phosphite, tris(nonylphenyl) phosphite, tris(dinonylphenyl) phosphite, dinonylphenyl-o-biphenyl phosphite, etc. (triC1-18 alkyl phosphite, etc.)] (-18alkyl-aryl) phosphites, 2,2-methylene bis(4,6-di-tert-butylphenyl)octyl phosphites, etc.), aliphatic carboxylic acid phosphites (tristearate phosphites, etc., C1-18 aliphatic carboxylic acid phosphites, etc.), phosphites containing epoxide units (poly(dipropylene glycol) nonylphenyl phosphites, tetraphenyl dipropylene glycol phosphites, etc.), phosphites containing cyclic neopentane units [bis(octadecyl pentaerythritol) bisphosphites, bis(2,4-di-tert-butylphenyl) pentaerythritol] Tetraol diphosphites, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphites, etc.; diphosphites (diisodecyl pentaerythritol diphosphites, bis(dodecyl) pentaerythritol diphosphites, 4,4'-isopropylidene diphenyl bis(dodecyl) diphosphites, etc.); triphosphites (heptapoly(dipropylene glycol) triphosphites, hexa-tridecyl-1,1,3-tris(3-tert-butyl-6-methyl-4-oxyphenyl)-3-methylpropane triphosphites, etc.). These phosphite compounds can be used alone or in combination of two or more.

[0396] Among them, when using polycarbonate resin, polyester resin, polyamide resin, polyacetal resin, etc. as thermoplastic resin (E), and using resins containing carbonate bonds, ester bonds, amide bonds, or acetal bonds in the polymer structural unit, from the viewpoint of suppressing the reduction of the resistance of these thermoplastic resins to hygrothermal decomposition, it is preferable to use phosphorus-based stabilizers with high hydrolysis resistance.

[0397] Preferably, a phosphite compound has 1 phosphorus atom in one molecule and 8 or more carbon atoms in each ester portion (in the case of multiple ester portions forming a ring, the total number of carbon atoms in the region sandwiched by the ester bond is taken as the number of carbon atoms in each portion). Alternatively, a phosphite compound having multiple phosphorus atoms in one molecule and 8 or more carbon atoms in the ester portion between each phosphorus element is preferred. Examples include triC6-18 alkyl phosphites (such as triisodecyl phosphite), phosphites containing branched C3-6 alkyl groups (such as tert-butyl) [tris(2,4-tert-butylphenyl) phosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, etc.], and tetraalkyl(C12-15)-4,4'-isopropylidene diphenyl diphosphite, etc.

[0398] Relative to 100% by mass of the resin composition, the content of the phosphorus stabilizer is preferably 0.001% by mass or more, more preferably 0.003% by mass or more, and preferably 2% by mass or less, more preferably 1% by mass or less. If the content of the phosphorus stabilizer is at or above the lower limit, the heat stabilization effect is better; if it is at or below the upper limit, the resin decomposition and the decrease in resistance to hygrothermal decomposition of the resin composition during melt mixing can be further suppressed.

[0399] In this resin composition, when phenolic stabilizers, sulfur-based stabilizers, and / or phosphorus-based stabilizers are used in combination, the total added mass of sulfur-based and phosphorus-based stabilizers is preferably 0.1 times or more, more preferably 0.2 times or more, and on the other hand, preferably 5 times or less, more preferably 3 times or less, relative to the added mass of phenolic stabilizers. If the content of sulfur-based and phosphorus-based stabilizers is at or above the aforementioned lower limit, the effect of improving heat aging resistance is more excellent; if it is at or below the aforementioned upper limit, the resin decomposition of the resin composition during melt mixing can be further suppressed.

[0400] When this resin composition contains phenolic stabilizers, sulfur-based stabilizers, and / or phosphorus-based stabilizers, the total content of stabilizers relative to 100% by mass of the resin composition is preferably 2% by mass or less. By keeping the total stabilizer content at 2% by mass or less, resin decomposition can be further suppressed during melt mixing.

[0401] Examples of inorganic pigments include iron oxide, ultramarine, titanium dioxide, and carbon black. Examples of organic pigments include phthalocyanine or anthraquinone blue pigments, perylene or quinacridone red pigments, and isoindolinone yellow pigments. Additionally, examples of specialty pigments include fluorescent pigments, metallic pigments, and pearl pigments. Examples of dyes include aniline black, violet ketones, and anthraquinone dyes. These pigments and dyes are available in various grades on the market, depending on the desired color. They can be used individually or in combination of two or more.

[0402] The ratio of polymer particle cluster (C) or the composition to 100% by mass of the resin composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 2% by mass or more. On the other hand, it is preferably 60% by mass or less, more preferably 50% by mass or less. If the ratio of polymer particle cluster (C) or the composition is at or above the lower limit mentioned above, the resulting molded article has better impact strength. If it is at or below the upper limit mentioned above, the decrease in the flowability or heat distortion temperature of the resin composition can be suppressed.

[0403] The ratio of thermoplastic resin (E) to 100% by mass of the resin composition is preferably 40% by mass or more, more preferably 50% by mass or more, and on the other hand, preferably 99.5% by mass or less, more preferably 99% by mass or less, and even more preferably 98% by mass or less. If the ratio of thermoplastic resin (E) is at or above the lower limit mentioned above, the decrease in the flowability or heat distortion temperature of the resin composition can be suppressed, and if it is at or below the upper limit mentioned above, the impact strength of the resulting molded article is more excellent.

[0404] (Method for manufacturing the resin composition)

[0405] The resin composition can be manufactured by mixing a group of polymer particles (C) or the composition itself, a thermoplastic resin (E), and additives as needed.

[0406] There are no particular limitations on the methods for mixing various materials, which can be known. For example, methods such as mixing and kneading using a rotary drum, V-type mixer, super mixer, Nota mixer, Banbury internal mixer, kneading roller, extruder, etc.

[0407] As an example of a method for manufacturing the resin composition of the present invention, one can exemplify a method in which polymer particle clusters (C) or the present composition, granular thermoplastic resin (E) and desired additives are mixed using an extruder, extruded into a filament, and cut into granules using a rotary cutter or the like. By this method, a granular resin composition can be obtained.

[0408] [molded body]

[0409] One aspect of the molded article of the present invention (hereinafter also referred to as "the molded article") comprises a group of polymer particles (C).

[0410] This molded body may also contain component (D).

[0411] This molded body may also contain thermoplastic resin (E).

[0412] This molded article is preferably composed of the above-described resin composition.

[0413] This molded article can be manufactured, for example, by molding a group of polymer particles (C), the composition, or the resin composition.

[0414] Examples of molding methods include those commonly used in the molding of thermoplastic resin compositions, such as injection molding, extrusion molding, blow molding, and calendering.

[0415] This molded material can be widely used in various industries, including automotive, office automation (OA) equipment, home appliances, electrical and electronic products, construction, consumer and cosmetic products, and medical supplies. More specifically, it can be used as frames, various components, coating materials, automotive structural components, automotive interior components, light reflectors, building structural components, and door and window sashes. More specifically, it can be used as computer frames, mobile phone frames, portable information terminal frames, portable game console frames, printer and copier interior and exterior components, conductive coating materials, automotive interior and exterior components, building exterior materials, resin window frame components, flooring materials, and piping components.

[0416] Other aspects of the present invention are shown below.

[0417] [1] A polymer containing a polyorganosiloxane is a polymer (A) composed of a polymer (A1) containing a polyorganosiloxane (A1) and a first vinyl polymer (A2) and a second vinyl polymer (B).

[0418] When the polymer containing polyorganosiloxane is dispersed in a liquid epoxy resin and cured to form a resin sheet, and its cross-section is observed with a transmission electron microscope, the polymer (A) has an island structure in which the polyorganosiloxane (A1) is the sea component and the first vinyl polymer (A2) is the island component. When the diameter of the particles of the polymer containing polyorganosiloxane is set to L and the maximum length of the polyorganosiloxane (A1) region contained in the particles is set to M, the ratio of the number of particles satisfying the following formula (1) relative to the total number of particles is less than 60%.

[0419] M / L>0.1…(1)

[0420] [2] According to [1], the ratio of the polyorganosiloxane (Al) to 100% by mass of the polymer containing the polyorganosiloxane is more than 1% by mass and less than 50% by mass.

[0421] [3] The polymer containing polyorganosiloxane according to [1] or [2] has a ratio of more than 1% by mass and less than 10% by mass of the polyorganosiloxane (Al) relative to 100% by mass of the polymer containing polyorganosiloxane.

[0422] [4] The polymer containing polyorganosiloxane according to any one of [1] to [3] has a number average particle size of 10 nm or more and 150 nm or less.

[0423] [5] The polymer containing a polyorganosiloxane according to any one of [1] to [4], wherein a portion of the polymer containing the polyorganosiloxane is insoluble in tetrahydrofuran, and the ratio of the polymer containing the polyorganosiloxane that is insoluble in tetrahydrofuran to 100% by mass of the polymer particle group containing the polyorganosiloxane is 80% by mass or more but less than 100% by mass.

[0424] [6] The polymer containing a polyorganosiloxane according to any one of [1] to [5], wherein a portion of the polymer containing the polyorganosiloxane is soluble in tetrahydrofuran, and the weight-average molecular weight of the polymer containing the polyorganosiloxane soluble in tetrahydrofuran is more than 20,000 and less than 500,000.

[0425] [7] The polymer containing polyorganosiloxane according to any one of [1] to [6], wherein in the island structure, the polyorganosiloxane (A1) region contains a plurality of the first vinyl polymer (A2) regions.

[0426] [8] The polymer containing polyorganosiloxane according to any one of [1] to [7] is dispersed in a liquid epoxy resin and cured to form a resin sheet. When its cross-section is observed with a transmission electron microscope, the polymer containing polyorganosiloxane has an island structure in which the polyorganosiloxane (A1) is used as the sea component, the first vinyl polymer (A2) is used as the first island component, and the second vinyl polymer (B) is used as the second island component.

[0427] [9] The polymer containing polyorganosiloxane according to any one of [1] to [8], wherein the ratio of polymer (A) to 100% by mass of the polymer containing polyorganosiloxane is 60% by mass or more and 95% by mass or less.

[0428]

[10] The polymer containing polyorganosiloxane according to any one of [1] to [9], wherein the vinyl monomer component (a2) constituting the first vinyl polymer (A2) contains (meth)acrylate monomer.

[0429]

[11] The polymer containing polyorganosiloxane according to any one of [1] to

[10] , wherein the vinyl monomer component (b) constituting the second vinyl polymer (B) contains at least one selected from the group consisting of (meth)acrylate monomers and aromatic vinyl monomers,

[0430] The total ratio of the (meth)acrylate monomer and the aromatic vinyl monomer is 50% or more relative to 100% by mass of the vinyl monomer component (b).

[0431]

[12] The polymer containing polyorganosiloxane according to any one of [1] to

[11] , wherein the vinyl monomer component (b) constituting the second vinyl polymer (B) contains methyl methacrylate,

[0432] The ratio of methyl methacrylate to the vinyl monomer component (b) is 50% by mass or more.

[0433]

[13] The polymer containing polyorganosiloxane according to any one of [1] to

[12] , wherein the polymer (A) is a polymer formed by polymerizing the vinyl monomer component (a2) constituting the first vinyl polymer (A2) in the presence of a latex containing the polyorganosiloxane (A1).

[0434]

[14] A composition comprising the polymer containing polyorganosiloxane as described in any one of [1] to

[13] , and at least one component selected from the group consisting of phosphoric acid compounds and their alkali metal salts.

[0435]

[15] According to the composition of

[14] , the alkali metal salt of the phosphoric acid compound is at least one selected from the group consisting of alkali metal salts of alkyl phosphoric acid and alkali metal salts of alkylaryl phosphoric acid.

[0436]

[16] According to the composition of

[14] or

[15] , wherein the alkali metal salt of the phosphoric acid compound is an alkali metal salt of polyoxyalkylene ether phosphoric acid.

[0437]

[17] The composition according to any one of

[14] to

[16] has a ratio of phosphorus atoms in the component of 100 ppm or more relative to 100 ppm of the total mass of the polymer containing the polyorganosiloxane and at least one component selected from the group consisting of the phosphoric acid compound and its alkali metal salt.

[0438]

[18] A resin composition comprising the polymer containing polyorganosiloxane as described in any one of [1] to

[13] and a thermoplastic resin.

[0439]

[19] A resin composition comprising the composition described in any one of

[14] to

[17] and a thermoplastic resin.

[0440]

[20] According to the resin composition of

[18] or

[19] , the thermoplastic resin contains at least one selected from the group consisting of aromatic polycarbonate, polymethyl methacrylate, styrene-acrylonitrile copolymer, polyethylene terephthalate, polybutylene terephthalate, polyvinyl chloride, polyphenylene sulfide and polyacetal.

[0441]

[21] A molded body comprising the polymer containing polyorganosiloxane as described in any one of [1] to

[13] .

[0442] [Example]

[0443] The present invention will now be described in more detail through manufacturing examples and embodiments. Manufacturing examples 1-1 to 1-2, 2-1 to 2-20 are examples of manufacturing polyorganosiloxane (A1), polymer (A), polymer particle group (C), and composition. In addition, "parts" means "parts by mass", "%" means "% by mass", and "ppm" means "ppm by mass". Furthermore, various measurement methods are described below.

[0444] [Determination of solid components]

[0445] The mass w1 of polyorganosiloxane latex was dried in a hot air dryer at 180°C for 30 minutes. The mass w2 of the residue after drying was measured, and the solid content [%] was calculated by the following formula (e).

[0446] Solid content [%]=w2 / w1×100···(e)

[0447] [Particle size determination]

[0448] The "polyorganosiloxane (A1) latex" or "polymer particle cluster (C) latex" was diluted with deionized water to a solid component concentration of about 3% as a sample. The number-average particle size Dn and mass-average particle size Dw were measured using the CHDF2000 particle size analyzer manufactured by MATEC Corporation of the United States under the following conditions.

[0449] Cartridge: A dedicated capillary cartridge for particle separation (trade name: C-202).

[0450] Carrier fluid: Dedicated carrier fluid (trade name: 2XGR500)

[0451] Liquidity of carrier liquid: Neutral

[0452] Flow rate of the carrier fluid: 1.4 ml / min

[0453] Carrier fluid pressure: approximately 4,000 psi (2,600 kPa)

[0454] Measurement temperature: 35℃

[0455] Sample volume used: 0.1 ml

[0456] [Powder Recovery Methods]

[0457] The recovery of polymer particle clusters (C) powder is carried out by either the flocculation method described below (referred to as G in Tables 1 and 2) or the spray recovery method (referred to as S in Tables 1 and 2).

[0458] Flocculation method: 630 parts of a 0.8% calcium acetate aqueous solution are heated to 50°C and stirred while polymer particle cluster (C) latex is slowly added dropwise to the aqueous solution to cause coagulation. The obtained polymer particle cluster (C) is filtered, washed, dehydrated, and dried to obtain polymer particle cluster (C) powder.

[0459] Spray drying method: The polymer particle group (C) latex is spray dried using an atomizer-type spray dryer (manufactured by Okawahara Chemical Machinery Co., Ltd., L8 spray dryer) under the following treatment conditions to obtain polymer particle group (C) powder.

[0460] <Spray drying processing conditions>

[0461] Spraying method: Rotary disc

[0462] Disk rotation speed: 25000 rpm

[0463] Hot air temperature: Inlet temperature: 130℃, Outlet temperature: 60℃

[0464] [Determination of THF insoluble components]

[0465] For the polymer particle group (C), the THF insoluble components were determined according to the following method.

[0466] (1-1) Add 0.5g of sample to 50mL (44.5g) of THF to prepare a mixed solution. After standing at 25℃ for 8 hours, stir with a stirrer for 30 minutes to dissolve the THF soluble components.

[0467] (1-2) The mixed solution was placed in a centrifuge tube whose mass was measured, and the liquid containing THF insoluble components and THF soluble components was separated by centrifugation (16000 rpm, 4 hours).

[0468] (1-3) After separating the supernatant containing THF-soluble components, add THF and stir. Then, centrifuge again in the same way as (1-2) above to wash away the THF-insoluble components.

[0469] (1-4) Repeat (1-3) twice and remove the supernatant. Immerse the centrifuge tube containing the THF-insoluble component in a warm water bath (80°C, 8 hours) to allow the THF to evaporate. Then, vacuum dry at 65°C for 6 hours to obtain a dried sample (the THF-insoluble component adhering to the centrifuge tube).

[0470] (1-5) Determine the mass of the obtained dried sample (THF insoluble component + centrifuge tube), and calculate the ratio w of the THF insoluble component using the following formula (f). ais (%).

[0471] w ais =(w c1 -w as ) / wt×100···(f)

[0472] wt: Mass of the polymer particle group (C) used in the determination

[0473] w as quality of centrifuge tubes

[0474] w c1 Mass of THF-insoluble components (including the mass of the centrifuge tube).

[0475] [Determination of the weight-average molecular weight of THF soluble components]

[0476] The weight-average molecular weight of the THF soluble component was determined by performing the following operations (2-1) to (2-3).

[0477] (2-1) The liquid containing THF soluble components collected in the above "Determination of THF insoluble components" was subjected to vacuum distillation using a rotary evaporator to remove THF and obtain the THF soluble components.

[0478] (2-2) Dissolve the THF soluble component obtained in (2-1) again in THF to make the sample concentration 0.1-0.3% to obtain a THF solution containing the THF soluble component.

[0479] (2-3) The THF solution containing the THF soluble component obtained in (2-2) above was determined by gel permeation chromatography (GPC), and the weight-average molecular weight (Mw) was obtained from the standard curve of standard polystyrene.

[0480] The GPC measurement conditions are as described in the examples below.

[0481] Device: HLC8220 manufactured by Tosoh Corporation

[0482] Chromatographic column: TSKgel SuperMultipore HZ-H manufactured by Tosoh Corporation (4.6 mm inner diameter × 15 cm length × 2 columns, exclusion limit 4 × 10⁻⁶).7 (presumption)

[0483] Elution buffer: THF

[0484] Elution buffer flow rate: 0.35 mL / min

[0485] Measurement temperature: 40℃

[0486] Sample injection volume: 10 μL

[0487] [TEM Image Acquisition and Image Analysis]

[0488] The polymer particle group (C) was placed into a polyethylene capsule, and liquid epoxy resin (Epiform R-2100, H-105, manufactured by Somar) was injected and stirred. The capsule was then placed at 25°C for 12 hours to allow the epoxy resin to cure. The resulting resin slices were then trimmed using a Leica EM UC7 ultramicrotome (manufactured by Leica Microsystems).

[0489] The obtained resin slides were stained with an osmium tetroxide aqueous solution (23°C, 12 hours) and then stained with a ruthenium tetroxide aqueous solution (23°C, 5 hours). The stained resin slides were then cut into sections at a cutting temperature of 23°C, a cutting speed of 0.4 mm / s, and a section thickness of 50 nm, and recycled onto a copper grid with a support film.

[0490] Using a TEM (Hitachi, H-7600), at an accelerating voltage of 80 kV and a magnification of 200,000x, randomly selected 0.5 μm areas on the surface of the recovered slices were observed. 2 TEM images were obtained within the above-mentioned area. In the obtained TEM images, the cured epoxy resin region (resin region) and the particle region dispersed within it were observed. Furthermore, within the particle region, the polyorganosiloxane (Al) portion was identified using light contrast, while the vinyl polymer portion was identified using dark contrast.

[0491] In a single TEM image, the particle regions observed are excluded from those that meet the criteria (i) to (iii) below.

[0492] (i) Particle regions truncated at the edges of the image.

[0493] (ii) Particle regions with a size less than 80% of the average particle size.

[0494] (iii) A particle region that has adjacent particle regions in three or more directions, and whose boundaries are unclear.

[0495] For the remaining particle regions, representing more than 80% and more than 50 particle regions, the contrast line contours are measured in the following order, the Z values ​​are calculated, and their average values ​​are obtained. The ratio of selected particle regions refers to the proportion of the number of selected particle regions relative to the total number of identifiable particle regions in the image.

[0496] Based on the obtained TEM images, the diameter L of the particle region and the maximum length M of the polyorganosiloxane (Al) region were calculated using image analysis software (ImageJ).

[0497] As described above, the diameter L of the particle region is determined by constructing a line profile by connecting the midpoints of the major and minor axes of the particle region and cutting off the particle diameter.

[0498] As mentioned above, the maximum length M is determined by the region with the maximum continuous length among the regions that continuously represent more than 75% of the maximum values ​​in a particle region obtained from the line profile, based on the contrast value (GrayValue).

[0499] Based on the obtained diameter L and maximum length M, the number of particle regions that satisfy the following formula (1) is defined as Z1, and the number of particle regions that do not satisfy the formula is defined as Z2. The Z value [%] is calculated according to the following formula (2).

[0500] M / L>0.1···(1)

[0501] Z value [%] = {Z1 / (Z1+Z2)}×100···(2).

[0502] <Manufacturing Example 1-1> (Manufacturing of Polyorganosiloxane (A1-1))

[0503] A mixture of 98 parts of cyclic organosiloxanes (manufactured by Shin-Etsu Silicones, product name: DMC, a mixture of 3- to 6-membered ring cyclic organosiloxanes) and 2 parts of 3-methacryloyloxypropylmethyldimethoxysilane (manufactured by Shin-Etsu Silicones, product name: KBM-502) was mixed to obtain a 100-part organosiloxane mixture. An aqueous solution containing 0.7 parts of sodium dodecylbenzenesulfonate (DBSNa, manufactured by Kao Corporation, product name: Neopelex G-15, solids conversion) dissolved in 300 parts of deionized water was added to the above mixture. The mixture was stirred at 10,000 rpm for 5 minutes using a homogenizer and then passed through a homogenizer twice under a pressure of 20 MPa to obtain a stable premixed emulsion.

[0504] Next, in a separable flask with a capacity of 5 liters and equipped with a cooling condenser, an aqueous solution containing 15 parts of dodecylbenzenesulfonic acid (DBSH, manufactured by Kao Corporation, product name: Neopelex GS) was added to 90 parts of deionized water. The aqueous solution was heated to 80°C, and the above emulsion was continuously added over 240 minutes to carry out the polymerization reaction. After cooling to 25°C, a 5% sodium hydroxide aqueous solution was added to neutralize the reaction solution to pH 7.0, yielding polyorganosiloxane latex (A1-1).

[0505] The solids content of the polyorganosiloxane latex (A1-1) is 20%. Furthermore, the number-average particle size (Dn) of this latex, as determined by a capillary particle size analyzer, is 26 nm, the mass-average particle size (Dw) is 35 nm, and the Dw / Dn ratio is 1.35.

[0506] <Manufacturing Examples 1-2>

[0507] (Manufacturing of polyorganosiloxane (A1-2))

[0508] 98 parts of a cyclic organosiloxane mixture (manufactured by Shin-Etsu Silicon Co., Ltd., product name: DMC, a mixture of 3- to 6-membered ring cyclic organosiloxanes) and 2 parts of 3-methacryloyloxypropylmethyldimethoxysilane (KBM-502) were mixed to obtain 100 parts of an organosiloxane mixture. An aqueous solution of 0.7 parts of sodium dodecylbenzenesulfonate (DBSNa) dissolved in 350 parts of deionized water was added to the mixture. The mixture was stirred at 10,000 rpm for 5 minutes using a homogenizer, and then passed through a homogenizer twice under a pressure of 20 MPa to obtain a stable premixed emulsion.

[0509] Next, in a 5-liter separable flask equipped with a cooling condenser, an aqueous solution containing 4 parts dodecylbenzenesulfonic acid (DBSH) was added to 40 parts deionized water. The aqueous solution was then heated to 80°C. The emulsion was then continuously added over 240 minutes to allow it to polymerize. The mixture was then cooled to 25°C, and 5% sodium hydroxide aqueous solution was added to neutralize the reaction solution to pH 7.0, yielding polyorganosiloxane latex (A1-2).

[0510] The solid content of the polyorganosiloxane latex (A1-2) is 18% by mass. In addition, the number-average particle size (Dn) of the latex, obtained by capillary particle size analyzer, is 67 nm, the mass-average particle size (Dw) is 83 nm, and the Dw / Dn ratio is 1.24.

[0511] <Manufacturing Example 2-1>

[0512] (Manufacturing of polymer particle swarms (C-1))

[0513] Eighteen parts (equivalent to 3.0 parts polymer) of the polyorganosiloxane latex (A1-1) obtained in Manufacturing Example 1-1 were collected into a 5-liter separable flask, and 170 parts of deionized water were added and mixed. Next, 76.6 parts of n-butyl acrylate (nBA), 0.4 parts of allyl methacrylate (AMA), and 0.3 parts of sodium dodecylbenzenesulfonate (DBSNa) were added to the separable flask. A nitrogen flow was introduced to replace the atmosphere in the flask, and the liquid temperature was raised to 43°C and stirred for 1 hour.

[0514] Add 0.15 parts of potassium persulfate (KPS) to start free radical polymerization. After stirring for 10 hours and confirming the polymerization heating peak, cool to 25°C and maintain for 15 hours to end the polymerization and obtain composite rubber latex.

[0515] The composite rubber latex was heated to 80°C, and 20 parts of methyl methacrylate (MMA) were added dropwise to the latex at a rate of 0.6 parts / minute to initiate the graft polymerization reaction. After the addition was completed, the temperature was maintained at 80°C for 1 hour, and then cooled to 25°C to obtain polymer particle cluster (C-1) latex.

[0516] The latex has a solid content of 35% and a polymerization rate of over 99.9%. This polymerization rate is the polymerization rate of the monomer components used in all processes from the manufacture of the composite rubber to graft polymerization. The number-average particle size (Dn) of the latex, obtained by capillary particle size analyzer, is 94 nm, the mass-average particle size (Dw) is 105 nm, and the Dw / Dn ratio is 1.12.

[0517] Next, the polymer particle cluster (C-1) powder was obtained through the above flocculation method. The THF-insoluble component of the polymer particle cluster (C-1) was 95%. In addition, the weight-average molecular weight of the THF-soluble component was 230,000.

[0518] like Figure 2 As shown, the polymer particle group (C-1) has an island structure with polyorganosiloxane (A1) as the sea component and vinyl polymer (A2) as the island component. Additionally, the Z-value is 8%.

[0519] <Manufacturing Example 2-2>

[0520] (Manufacturing of polymer particle swarms (C-2))

[0521] The latex of polymer particle group (C-1) obtained in Manufacturing Example 2-1 was subjected to powder recovery by the spray drying method described above, thereby obtaining polymer particle group (C-2). Since it is the same latex after polymerization, the particle size, the ratio of THF insoluble components, the weight-average molecular weight of THF soluble components, and the Z value are the same as those of polymer particle group (C-1).

[0522] <Manufacturing Examples 2-3 to 2-6>

[0523] (Manufacturing of polymer particle clusters (C-3) to (C-6))

[0524] Except for changes to the amount of monomer used and the powder recovery method as described in Table 1, polymer particle groups (C-3) to (C-6) were obtained in the same manner as in Manufacturing Example 2-1. The agglomeration temperature during the flocculation process was appropriately varied between 50 and 85°C to match the resulting powder properties.

[0525] <Manufacturing Example 2-7>

[0526] (Manufacturing of polymer particle swarms (C-7))

[0527] Eighteen parts (equivalent to 3.0 parts polymer) of the polyorganosiloxane latex (A1-1) obtained in Manufacturing Example 1-1 were collected into a 5-liter separable flask, and 170 parts of deionized water were added and mixed. Next, 66.0 parts of n-butyl acrylate (nBA), 1.0 part of allyl methacrylate (AMA), and 0.3 parts of sodium dodecylbenzenesulfonate (DBSNa) were added to the separable flask. A nitrogen flow was introduced to replace the atmosphere in the flask, and the liquid temperature was raised to 43°C and stirred for 1 hour.

[0528] Add 0.15 parts of potassium persulfate (KPS) to start free radical polymerization. After stirring for 10 hours and confirming the polymerization heating peak, cool to 25°C and maintain for 15 hours to end the polymerization and obtain composite rubber latex.

[0529] The composite rubber latex was heated to 80°C, and 7.5 parts of methyl methacrylate (MMA) were added dropwise to the latex at a rate of 0.6 parts / min to initiate the graft polymerization reaction. After the addition was complete, the temperature was maintained at 80°C for 1 hour. Then, 0.04 parts of potassium persulfate (KPS) were added and stirred for 15 minutes. A mixed solution of 5.6 parts of acrylonitrile (AN), 16.9 parts of styrene (St), and 0.015 parts of n-octyl mercaptan (nOM) was added dropwise to the latex at a rate of 0.3 parts / min to initiate the graft polymerization reaction again. After the addition was complete, the temperature was maintained at 80°C for 2 hours, and then 0.04 parts of potassium persulfate (KPS) were added. After stirring for another 2 hours, the mixture was cooled to 25°C to obtain the polymer particle cluster (C-7) latex.

[0530] The latex has a solid content of 35% and a polymerization rate of over 99.9%. This polymerization rate is the polymerization rate of the monomer components used in all processes from the manufacture of the composite rubber to graft polymerization. The number-average particle size (Dn) of the latex, obtained by capillary particle size analyzer, is 90 nm, the mass-average particle size (Dw) is 112 nm, and the Dw / Dn ratio is 1.25.

[0531] Next, the polymer particle group (C-7) powder was obtained by the above flocculation method. The THF-insoluble component of the polymer particle group (C-7) was 95% by mass. In addition, the weight-average molecular weight of the THF-soluble component was 400,000.

[0532] like Figure 6 As shown, the polymer particle group (C-7) has an island structure with polyorganosiloxane (A1) as the sea component and vinyl polymer (A2) as the island component. Additionally, the Z-value is 8%.

[0533] <Manufacturing Example 2-8>

[0534] (Manufacturing of polymer particle swarms (C-8))

[0535] Except for changing the amount of monomers used as described in Table 1, similar to manufacturing examples 2-7, a powder of polymer particle group (C-8) was obtained.

[0536] <Manufacturing Examples 2-9, 2-10>

[0537] (Preparation of compositions (C-9) and (C-10))

[0538] In the polymer particle group (C-1) latex obtained in Manufacturing Example 2-1, sodium tridecyloxyethylene phosphate (RS-610Na, manufactured by Toho Chemical Industry Co., Ltd., product name: Phosphhanol (registered trademark) RS-610Na, solid component conversion, polyoxyethylene alkyl phosphate with tridecyl alkyl group, number of oxyethylene units in polyoxyethylene: 6) in the amount listed in Table 1 was added as component (D) to obtain composition (C-9) latex and composition (C-10) latex.

[0539] Then, the latexes are pulverized by the above flocculation method to obtain powder of composition (C-9) and powder of composition (C-10).

[0540] In compositions (C-9) and (C-10), the THF-insoluble component of the polymer particle group (C-1) is 95%, the weight-average molecular weight of the THF-soluble component is 230,000, and the Z-value is 8%.

[0541] The phosphorus atom content relative to the total mass of the polymer particle group (C-1) and the added emulsifier is 230 ppm in composition (C-9) and 490 ppm in composition (C-10). Furthermore, the polymer (C-1) obtained in Manufacturing Example 2-1 has a phosphorus atom content of less than 16 ppm.

[0542] <Manufacturing Examples 2-11, 2-12>

[0543] (Manufacturing of polymer particle clusters (C-11) and (C-12))

[0544] Except for changing the types and amounts of the polyorganosiloxane latex, monomers, and emulsifiers used as described in Table 2, similar to Manufacturing Example 2-1, powders of polymer particle groups (C-11) and (C-12) were obtained. The flocculation temperature used to obtain each powder was appropriately varied between 55 and 95°C.

[0545] <Manufacturing Examples 2-13 to 2-15>

[0546] (Manufacturing of polymer particle clusters (C-13) to (C-15))

[0547] The types and amounts of polyorganosiloxane latex, monomers, and emulsifiers used were changed as described in Table 2. Otherwise, similar to Manufacturing Examples 2-7, powders with polymer particle groups (C-13) to (C-15) were obtained. The flocculation temperature used to obtain each powder was appropriately varied between 55 and 75°C to obtain the powder properties.

[0548] <Manufacturing Example 2-16>

[0549] (Manufacturing of polymer particle swarms (C-16))

[0550] 5.0 parts of n-butyl acrylate (nBA), 0.03 parts of allyl methacrylate (AMA), 0.3 parts of sodium dodecylbenzenesulfonate (DBSNa) and 160 parts of deionized water were placed into a 5-liter separable flask. The atmosphere inside the flask was replaced with nitrogen by circulating nitrogen gas and stirring for 1 hour.

[0551] After heating the liquid to 80°C, add 0.05 parts of potassium persulfate (KPS), stir for 180 minutes, cool to 25°C, and let stand for 18 hours.

[0552] Next, 74.6 parts of n-butyl acrylate (nBA), 0.37 parts of allyl methacrylate (AMA), and 0.4 parts of sodium dodecylbenzenesulfonate (DBSNa) were added. While the nitrogen flow was circulating, the mixture was stirred at 25°C for 90 minutes. Then, the liquid temperature was raised to 43°C and stirred for 1 hour.

[0553] Add 0.15 parts of potassium persulfate (KPS) to start free radical polymerization. After stirring for 10 hours and confirming the polymerization heating peak, cool to 25°C and maintain for 15 hours to end the polymerization and obtain composite rubber latex.

[0554] The composite rubber latex was heated to 80°C, and 20 parts of methyl methacrylate (MMA) were added dropwise to the latex at a rate of 0.6 parts / minute to initiate the graft polymerization reaction. After the addition was completed, the temperature was maintained at 80°C for 1 hour, and then cooled to 25°C to obtain polymer particle cluster (C-16) latex.

[0555] The latex has a solid content of 35% and a polymerization rate of over 99.9%. This polymerization rate is the polymerization rate of the monomer components used in all processes from the manufacture of acrylic rubber to graft polymerization. The number-average particle size (Dn) of the latex, obtained by capillary particle size analyzer, is 88 nm, the mass-average particle size (Dw) is 94 nm, and the Dw / Dn ratio is 1.07.

[0556] Next, the polymer particle group (C-16) was pulverized using the aforementioned flocculation method to obtain powder. The THF-insoluble component ratio of the polymer particle group (C-16) was 96%. Furthermore, the weight-average molecular weight of the THF-soluble component was 170,000. Since the polymer particle group (C-16) is a polymer that does not contain polyorganosiloxanes (A1) and is only a vinyl polymer (A2), TEM observation was not performed.

[0557] <Manufacturing Example 2-17>

[0558] (Manufacturing of polymer particle swarm (C-17))

[0559] Except for the change in the amount of monomers used as described in Table 2, polymer particle cluster (C-17) latex was obtained in the same manner as in Manufacturing Example 2-1.

[0560] The latex has a solid content of 35% and a polymerization rate of over 99.9%. Furthermore, the number-average particle size (Dn) obtained by capillary particle size analyzer is 98 nm, the mass-average particle size (Dw) is 108 nm, and the Dw / Dn ratio is 1.11.

[0561] Next, the polymer particle group (C-17) was pulverized using the aforementioned flocculation method to obtain powder. The THF-insoluble component ratio of the polymer particle group (C-17) was 79%. Furthermore, the weight-average molecular weight of the THF-soluble component was 410,000. Additionally, the Z-value was 68%.

[0562] <Manufacturing Example 2-18>

[0563] (Manufacturing of polymer particle swarms (C-18))

[0564] Eighteen parts (equivalent to 3.0 parts polymer) of the polyorganosiloxane latex (A1-1) obtained in Manufacturing Example 1-1 were collected into a 5-liter separable flask, and 220 parts of deionized water were added and mixed. Next, 76.6 parts of n-butyl acrylate (nBA), 0.4 parts of allyl methacrylate (AMA), and 0.3 parts of sodium dodecylbenzenesulfonate (DBSNa) were added to the separable flask. The atmosphere inside the flask was replaced with nitrogen by circulating a nitrogen stream, the liquid temperature was raised to 65°C, and the mixture was stirred for 1 hour.

[0565] Add 0.25 parts of potassium persulfate (KPS) to start free radical polymerization. Then, raise the liquid temperature to 80°C and maintain it for 1 hour to complete the polymerization, obtaining a composite rubber latex.

[0566] While maintaining the latex temperature at 80°C, 20 parts of methyl methacrylate (MMA) were added dropwise to the latex at a rate of 0.6 parts / minute to initiate the graft polymerization reaction. After the addition was complete, the latex was maintained at 80°C for 1 hour and then cooled to 25°C to obtain polymer particle cluster (C-18) latex.

[0567] The solid content of the latex was 30% by mass, and the polymerization rate was over 99.9%. In addition, the number-average particle size (Dn) obtained by capillary particle size analyzer was 98 nm, the mass-average particle size (Dw) was 113 nm, and the Dw / Dn ratio was 1.16.

[0568] Next, 630 parts of an aqueous solution containing 0.8% calcium acetate were heated to 70°C. While stirring, the obtained graft copolymer latex was slowly added dropwise to the aqueous solution, allowing it to coagulate. The resulting graft copolymer was filtered, washed, dehydrated, and dried to obtain polymer particle cluster (C-18) powder. The THF-insoluble component of polymer particle cluster (C-18) was 93% by mass. Furthermore, the weight-average molecular weight of the THF-soluble component was 190,000. Additionally, the Z-value was 66%.

[0569] <Manufacturing Example 2-19>

[0570] (Manufacturing of polymer particle swarm (C-19))

[0571] Eighteen parts (equivalent to 3.0 parts polymer) of the polyorganosiloxane latex (A1-1) obtained in Manufacturing Example 1-1 were collected into a 5-liter separable flask, and 155 parts of deionized water were added and mixed. Next, 76.6 parts of n-butyl acrylate (nBA), 0.4 parts of allyl methacrylate (AMA), 0.15 parts of tert-butyl hydroperoxide (t-BH), and 0.3 parts of sodium dodecylbenzenesulfonate (DBSNa) were added to the separable flask. The atmosphere inside the flask was replaced with nitrogen by circulating a nitrogen stream, the liquid temperature was raised to 50°C, and the mixture was stirred for 1 hour.

[0572] Free radical polymerization was initiated by adding 5 parts of deionized water containing 0.0005 parts ferrous sulfate heptahydrate (Fe), 0.0015 parts ethylenediaminetetraacetic acid disodium salt dihydrate (EDTA), and 0.2 parts sodium formaldehyde sulfoxylate (SFS). The polymerization was then maintained for 1 hour to complete, yielding a composite rubber latex.

[0573] While maintaining the latex temperature at 50°C, a mixture of 20 parts methyl methacrylate (MMA) and 0.05 parts tert-butyl hydroperoxide (t-BH) was added dropwise to the latex at a rate of 0.6 parts / minute to initiate the graft polymerization reaction. After the addition was complete, the mixture was maintained at 50°C for 1 hour and then cooled to 25°C to obtain a polymer particle cluster (C-19) latex.

[0574] The latex has a solid content of 35% by mass and a polymerization rate of over 99.9%. Furthermore, the latex has a number-average particle size (Dn) of 96 nm, a mass-average particle size (Dw) of 106 nm, and a Dw / Dn ratio of 1.11, as determined by a capillary particle size analyzer.

[0575] Next, 630 parts of an aqueous solution containing 0.8% calcium acetate were heated to 70°C. While stirring, the obtained graft copolymer latex was slowly added dropwise to the aqueous solution, allowing it to coagulate. The resulting graft copolymer was filtered, washed, dehydrated, and dried to obtain polymer particle group (C-19) powder. The THF-insoluble component of polymer particle group (C-19) was 93% by mass. Furthermore, the weight-average molecular weight of the THF-soluble component was 170,000. Additionally, the Z-value was 96%.

[0576] <Manufacturing Example 2-20>

[0577] (Manufacturing of polymer particle swarm (C-20))

[0578] Except for the changes in the type and amount of monomers used as described in Table 2, a powder of polymer particle group (C-20) was obtained in the same manner as in Manufacturing Example 2-19. The THF-insoluble component of polymer particle group (C-20) was 85% by mass. In addition, the weight-average molecular weight of the THF-soluble component was 150,000. Furthermore, the Z-value was 68%.

[0579] [Table 1]

[0580]

[0581] [Table 2]

[0582]

[0583] <Examples 1-14, Comparative Examples 1-11>

[0584] The polymer obtained in the above manufacturing example, styrene-acrylonitrile copolymer, carbon black (CB, manufactured by Mitsubishi Chemical Corporation, product name: #960B), and magnesium stearate (MgST, manufactured by Nacalai Tesk) were blended in the ratios shown in Tables 3 to 6 to obtain a mixture. This mixture was fed into a devolatilization twin-screw extruder (manufactured by Toshiba Machine Co., Ltd., TEM-35B (trade name)) heated to a barrel temperature of 240°C for compounding to produce granules of each resin composition.

[0585] Here, the following copolymer is used as a styrene-acrylonitrile copolymer.

[0586] SAN-1: Manufactured by Techno UMG, product name: SR-56B (AN content 33%)

[0587] SAN-2: Manufactured by Techno UMG, product name: AP-H (AN content 27%)

[0588] SAN-3: Manufactured by Techno UMG, Product Name: AP-A (AN content 30%)

[0589] AN content is the mass ratio of acrylonitrile units to 100% of the styrene-acrylonitrile copolymer.

[0590] Each granule was injection molded under the following conditions to produce test pieces for evaluation.

[0591] Injection molding machine: Sumitomo Heavy Industries, Ltd., SE100DU (product name)

[0592] Barrel temperature: 240℃, mold temperature: 80℃

[0593] Test piece specifications:

[0594] Test piece A: Length 80mm × Width 10mm × Thickness 4mm

[0595] Test piece B: Length 100mm × Width 50mm × Thickness 2mm

[0596] [Charpy Impact Strength]

[0597] For test piece A, a type A notch was etched according to ISO 179-1, and the Charpy impact strength was measured at 23℃ and -30℃. Generally speaking, the higher the value, the better the impact resistance, and the more desirable the material.

[0598] [Color Development Test]

[0599] As an indicator of color appearance, the lightness (based on L) of test piece B was measured using a spectrophotometer (NECST SE7700, manufactured by Nippon Denshoku Kogyo Co., Ltd.) under C light source and 2-degree field of view conditions, by means of reflected light measurement. * (JIS Z8781-4). In the embodiments of this application, since the coloring is black, it can be said that the lower the value, the better the coloring appearance (blackness), and the more preferred.

[0600] [Weather resistance test]

[0601] Using the same molded body (plate) as the above color development test, the weather resistance test was conducted under the following irradiation conditions.

[0602] "Irradiation conditions"

[0603] Test apparatus: Daipla Wintes, Daipla Metal Weather, model KW-R5TP-A, 5-tank temperature set at 50℃

[0604] UV irradiation conditions: set at 65mW / cm 2

[0605] The measurement was performed using a Ushio Electric Corporation UIT-101 / UVD-365PD illuminometer, with a measurement wavelength of 330–390 nm and a peak sensitivity wavelength of 365 nm.

[0606] Filter: KF-1 filter (transmission wavelength range: 295nm~780nm)

[0607] Test atmosphere: Irradiation for 20 hours, followed by darkness for 4 hours (24-hour cycle)

[0608] Test duration: 96 hours (4 cycles)

[0609] Using a spectrophotometer (manufactured by Nippon Denshoku Kogyo Co., Ltd., SE7700 (trade name)), under C light source and 2-degree field of view conditions, the yellowness (YI, based on JIS K7105) and lightness (L) before and after the weathering test were measured by the reflected light measurement method. * ) and chromaticity (a * b * (Based on JIS Z8781-4).

[0610] The yellowness (YI1) before the weathering test is the initial yellowness (YI).

[0611] The change in yellowness (ΔYI) is calculated from the yellowness before the weathering test (YI1) and the yellowness after the weathering test (YI2) using the following formula (g). In addition, the color difference (ΔE) *ab The lightness (L*1) and chromaticity (a*1, b*1) before the weathering test are determined by the lightness (L*1) and chromaticity (a*1, b*1) of the weathering test. * 1) and brightness (L) after weathering test * 2) and chromaticity (a) * 2. b * 2) Calculated using the following formula (h).

[0612] Formula (g): ΔYI=YI2-YI1

[0613] Equation (h): ΔE * ab =((L) * 2-L * 1)+(a * 2-a * 1)+(b * 2-b * 1)) 0.5

[0614] The lower the initial yellowness, the better the heat resistance and color change during molding, making it a preferred choice. Furthermore, the smaller the variation in yellowness and color difference, the better the weather resistance, also making it a preferred choice.

[0615] [Table 3]

[0616]

[0617] Examples 1-6 exhibit excellent impact strength and color appearance.

[0618] In Comparative Example 1, the impact strength was extremely low because it did not contain polymer particle clusters (C).

[0619] In Comparative Example 2, the impact strength was low because an acrylic polymer without polysiloxane was used.

[0620] In Comparative Examples 3 to 5, the impact strength and color appearance were low because polymer particle groups (C) with a Z value of 60% or more were used.

[0621] [Table 4]

[0622]

[0623] Examples 7-12 exhibit excellent impact strength and color appearance.

[0624] In Comparative Example 6, the impact strength and color appearance were low because a polymer particle group (C) with a Z value of 60% or more was used.

[0625] [Table 5]

[0626]

[0627] Example 13 exhibits excellent impact strength and color appearance.

[0628] In Comparative Examples 8 and 9, the impact strength and color appearance were low because polymer particle groups (C) with a Z value of 60% or more were used.

[0629] [Table 6]

[0630]

[0631] Example 14 exhibits excellent impact strength and weather resistance.

[0632] In Comparative Examples 10 and 11, since polymer particle groups (C) with a Z value of 60% or more were used, the impact strength, color appearance, heat resistance and weather resistance were low.

[0633] <Examples 15-25, Comparative Examples 12-19>

[0634] The polymers containing polyorganosiloxanes obtained in the above manufacturing examples, methacrylic acid resin (PMMA), and various organic dyes were combined in the ratios shown in Tables 7 and 8 to obtain mixtures. These mixtures were then fed into a devolatilization twin-screw extruder (Toshiba Machine Co., Ltd., TEM-35B (trade name)) heated to a barrel temperature of 250°C for compounding to produce granules of each resin composition.

[0635] Here, Acrypet VH001 (trade name, containing more than 90% methyl methacrylate units, manufactured by Mitsubishi Chemical Corporation) is used as the methacrylate resin (PMMA).

[0636] In addition, the following substances are used as colorants.

[0637] (OD-1): Organic dye, manufactured by Mitsubishi Chemical Corporation, Diaresin Green (ダイアレジングリーン) C

[0638] (OD-2): Organic dye, manufactured by Mitsubishi Chemical Corporation, Diaresin Red A

[0639] (OD-3): Organic dye, manufactured by Mitsubishi Chemical Corporation, Diaresin Blue G

[0640] CB: Carbon black, manufactured by Mitsubishi Chemical Corporation, #960B

[0641] The resin composition granules were injection molded under the following conditions to produce test pieces for evaluation.

[0642] Injection molding machine: Toshiba Machine Co., Ltd., EC20PNII (product name)

[0643] Barrel temperature: 250℃, mold temperature: 60℃

[0644] Test piece specifications:

[0645] Test piece A: Length 80mm × Width 10mm × Thickness 4mm

[0646] Test piece C: Length 50mm × Width 50mm × Thickness 3mm

[0647] [Charpy Impact Strength]

[0648] For test piece A, a type A notch was etched according to ISO 179-1, and the Charpy impact strength was measured at 23℃ and -30℃. Generally speaking, the higher the value, the better the impact resistance, and the more desirable the material.

[0649] [Color Development Test]

[0650] As an indicator of the color appearance of the resin composition, lightness (L*) was evaluated according to the following method. The hue of the above test piece C was measured using a spectrophotometer (trade name: SD7000, manufactured by Nippon Denshoku Kogyo Co., Ltd.) in SCE mode, and L* was determined according to ISO 11664-4. * In the embodiments of this application, since the coloring is black, it can be said that the lower the value, the better the coloring appearance (blackness), and the more preferred.

[0651] [Table 7]

[0652]

[0653] Examples 15-18 exhibit excellent impact strength and color appearance.

[0654] In Comparative Example 12, the impact strength was extremely low because it did not contain polymer particle clusters (C).

[0655] In Comparative Examples 13-15, since polymer particle groups (C) with a Z value of 60% or more were used, the balance between impact strength and color appearance was low.

[0656] [Table 8]

[0657]

[0658] Examples 19-25 exhibit excellent impact strength and color appearance.

[0659] In Comparative Example 16, the impact strength was extremely low because it did not contain polymer particle clusters (C).

[0660] In Comparative Examples 17-19, the impact strength and color appearance were low because polymer particle groups (C) with a Z value of 60% or more were used.

[0661] <Examples 26-31, Comparative Examples 20-34>

[0662] The polymers containing polyorganosiloxanes obtained in the manufacturing examples, various additives, and various thermoplastic resins were blended in the ratios shown in Tables 9-12 to obtain mixtures. These mixtures were then fed into a devolatilization twin-screw extruder (manufactured by Ikebe Corporation, PCM-30 (trade name)) for compounding to produce granules of each resin composition.

[0663] Here, the following thermoplastic resin is used as the thermoplastic resin.

[0664] PC: Polycarbonate resin (Iupilon S-2000F, manufactured by Mitsubishi Engineering Plastics, with an average molecular weight of 24,000).

[0665] SAN-2: Styrene-acrylonitrile copolymer (manufactured by AP-H and Techno-UMG).

[0666] PET: Polyethylene terephthalate resin (TRN8550FF, manufactured by Teijin Corporation).

[0667] PCGF-1: Polycarbonate resin with added glass fiber (Iupilon GS 2020MR2, manufactured by Mitsubishi Engineering Plastics, with 20% by mass glass fiber added).

[0668] The resin composition granules were injection molded to produce test pieces for evaluation.

[0669] Injection molding machine: Sumitomo Heavy Industries, Ltd., SE100DU (product name)

[0670] Test piece specifications:

[0671] Test piece A: Length 80mm × Width 10mm × Thickness 4mm

[0672] Test piece D: Length 127mm × Width 12.7mm × Thickness 1.6mm

[0673] At this point, the extrusion and injection molding conditions are as follows, and should be appropriately modified based on the fluidity of the molding resin.

[0674] (Example 26, Comparative Examples 20-22)

[0675] The extrusion barrel temperature is 280℃, the injection molding barrel temperature is 280℃, and the mold temperature is 80℃.

[0676] (Examples 27-28, Comparative Examples 23-26)

[0677] The extrusion barrel temperature is 260℃, the injection molding barrel temperature is 260℃, and the mold temperature is 80℃.

[0678] (Examples 29-30, Comparative Examples 27-30)

[0679] The extrusion barrel temperature is 280℃, the injection molding barrel temperature is 300℃, and the mold temperature is 70℃.

[0680] (Example 31, Comparative Examples 31-34)

[0681] The extrusion barrel temperature is 300℃, the injection molding barrel temperature is 300℃, and the mold temperature is 90℃.

[0682] [Charpy Impact Strength]

[0683] For test piece A, a type A notch was etched according to ISO 179-1, and the Charpy impact strength was measured. Generally speaking, a higher value indicates better impact resistance and is considered superior.

[0684] In addition, in this embodiment, some impact tests showed high impact resistance but incomplete fracture of the test piece. In such cases, since the correct impact value cannot be calculated, it is marked as NB in ​​the table.

[0685] [Table 9]

[0686]

[0687] In Example 26, the impact strength is excellent.

[0688] In Comparative Example 20, the impact strength was extremely low because it did not contain polymer particle clusters (C).

[0689] In Comparative Examples 21-22, the impact strength was low because a group of polymer particles (C) with a Z value of 60% or higher was used.

[0690] [Table 10]

[0691]

[0692] In Examples 27 and 28, the impact strength is excellent.

[0693] In Comparative Example 23, the impact strength was extremely low because it did not contain polymer particle clusters (C).

[0694] In Comparative Examples 24-26, the impact strength was low because a polymer particle group (C) with a Z value of 60% or higher was used.

[0695] [Table 11]

[0696]

[0697] In Examples 29 and 30, the impact strength is excellent.

[0698] In Comparative Example 27, the impact strength was extremely low because it did not contain polymer particle clusters (C).

[0699] In Comparative Examples 28-30, the impact strength was low because polymer particle groups (C) with a Z value of 60% or more were used.

[0700] [Table 12]

[0701]

[0702] In Example 31, the impact strength is excellent.

[0703] In Comparative Example 31, the impact strength is extremely low because it does not contain polymer particle clusters (C).

[0704] In Comparative Examples 32-34, the impact strength was low because a polymer particle group (C) with a Z value of 60% or higher was used.

[0705] <Examples 32-33, Comparative Examples 35-36>

[0706] The polymers containing polyorganosiloxanes obtained in the above manufacturing examples, various additives, and polyacetal resin (POM) were combined in the proportions shown in Table 13 to obtain a mixture. The mixture was fed into a devolatilization twin-screw extruder (manufactured by Ikegai Corporation, PCM-30 (trade name)) heated to a barrel temperature of 180°C for mixing to produce granules of each resin composition.

[0707] Here, HOSTAFORM C9021 (trade name, manufactured by Celanese Japan Co., Ltd.) was used as the polyacetal resin (POM).

[0708] In addition, the following additives are used as various adjuvants.

[0709] St-Ca: Calcium stearate (Calcium stearate GF-200, manufactured by Nippon Oil Company).

[0710] Irg245: Phenolic antioxidant (Irganox 245, manufactured by Ciba Japan).

[0711] The resin composition granules were injection molded under the following conditions to produce test pieces for evaluation.

[0712] Injection molding machine: Sumitomo Heavy Industries, Ltd., SE100DU (product name)

[0713] Barrel temperature: 205℃, mold temperature: 70℃

[0714] Test piece specifications:

[0715] Test piece A: Length 80mm × Width 10mm × Thickness 4mm

[0716] [Charpy Impact Strength]

[0717] For test piece A, a type A notch was marked according to ISO 179-1, and the Charpy impact strength was measured at 23℃ and -30℃. Generally speaking, the higher the value, the better the impact resistance, and the more desirable the material.

[0718] [Table 13]

[0719]

[0720] In Examples 32 and 33, the impact strength is excellent.

[0721] In Comparative Example 35, the impact strength was extremely low because it did not contain polymer particle clusters (C).

[0722] In Comparative Example 36, the impact strength was low because a polymer particle group (C) with a Z value of 60% or higher was used.

[0723] <Examples 34-35, Comparative Examples 37-38>

[0724] The polymers containing polyorganosiloxanes obtained in the above manufacturing examples and polyvinyl chloride resins were combined in the ratios shown in Table 14 to obtain a mixture.

[0725] Here, the polyvinyl chloride resin used was 100 parts of vinyl chloride resin (product name: TK-1000, manufactured by Shin-Etsu Chemical Industry Co., Ltd., average degree of polymerization 1050), 3 parts of Ca / Zn composite stabilizer (product name: HT-547A, manufactured by Nitto Kasei Corporation), 6 parts of calcium carbonate (product name: μ-powder 3S, manufactured by Bikawa Powder Chemical Industry Co., Ltd.), 3 parts of titanium dioxide (product name: TIPAQUER830, manufactured by Ishihara Sangyo Co., Ltd.), 0.5 parts of glycerol fatty acid ester (product name: Loxiol GH-4, manufactured by Imuroli Oil Chemicals Japan Co., Ltd.), 0.2 parts of polymer composite ester (product name: Loxiol VPN963, manufactured by Imuroli Oil Chemicals Japan Co., Ltd.), 0.3 parts of polymer composite ester (product name: Loxiol G70S, manufactured by Imuroli Oil Chemicals Japan Co., Ltd.), and polyethylene wax (product name: Loxiol... VPN233 (manufactured by Imuroy Oil Chemicals Japan Co., Ltd.) 0.2 parts, acrylic processing aid (product name: methylbutene P-570A, manufactured by Mitsubishi Chemical Co., Ltd.) were supplied to a Henschel mixer to obtain a powder that was uniformly mixed.

[0726] The mixture of the above-mentioned vinyl chloride resin and various polymers containing polyorganosiloxanes was melt-kneaded for 5 minutes at 190°C and a roll gap of 0.4 mm using a dielectric-heated 8-inch test roll (manufactured by Kansai Roller Co., Ltd.) to obtain a sheet-like molded body. The obtained sheet-like molded body was then hot-pressed for 5 minutes at 190°C and 15 MPa using a hot press (manufactured by Shoji Co., Ltd.) to obtain a molded body with a thickness of 4 mm. The following test pieces were cut from the obtained molded body for evaluation.

[0727] Test piece A: Length 80mm × Width 10mm × Thickness 4mm.

[0728] [Charpy Impact Strength]

[0729] For test piece A, a type A notch was marked according to ISO 179-1, and the Charpy impact strength was measured at 23°C and -10°C. Generally, a higher value indicates better impact resistance and is preferred. However, in this embodiment, some impact tests showed high impact resistance but incomplete fracture of the test piece. In such cases, since the correct impact value cannot be calculated, it is marked as NB in ​​the table.

[0730] [Table 14]

[0731]

[0732] In Examples 34 and 35, the impact strength is excellent.

[0733] In Comparative Example 37, the impact strength was extremely low because it did not contain polymer particle clusters (C).

[0734] In Comparative Example 38, the impact strength was low because a polymer particle group (C) with a Z value of 60% or higher was used.

[0735] <Example 36, Comparative Examples 39-40>

[0736] The polymers containing polyorganosiloxanes obtained in the above manufacturing examples and polyamide resins (PA) were blended in the proportions shown in Table 15 to obtain mixtures. After drying the mixtures at 80°C for 12 hours, they were fed into a devolatilization twin-screw extruder (manufactured by Ikegai Corporation, PCM-30 (trade name)) heated to a barrel temperature of 250°C for mixing to produce granules of each resin composition.

[0737] Here, UBE Nylon 1022B (trade name, polyamide 6, manufactured by Ube Industries, Inc.) is used as the polyamide resin (PA).

[0738] The resin composition granules were injection molded under the following conditions to produce test pieces for evaluation.

[0739] Injection molding machine: Sumitomo Heavy Industries, Ltd., SE100DU (product name)

[0740] Barrel temperature: 250℃, mold temperature: 80℃

[0741] Test piece specifications:

[0742] Test piece A: Length 80mm × Width 10mm × Thickness 4mm

[0743] [Charpy Impact Strength]

[0744] For test piece A, a type A notch was etched according to ISO 179-1, and the Charpy impact strength under oven-dry conditions was measured at 23℃ and -40℃. It can be said that the higher the value, the better the impact resistance, and the more desirable the material.

[0745] [Table 15]

[0746]

[0747] In Example 36, the impact strength is excellent.

[0748] In Comparative Example 39, the impact strength was extremely low because it did not contain polymer particle clusters (C).

[0749] In Comparative Example 40, the impact strength was low because a polymer particle group (C) with a Z value of 60% or higher was used.

[0750] <Example 37, Comparative Examples 41-42>

[0751] The polyorganosiloxane polymers and polylactic acid resin (PLA) obtained in the above manufacturing examples were blended in the ratios shown in Table 16 to obtain a mixture. The mixture was fed into a devolatilization twin-screw extruder (manufactured by Ikegai Corporation, PCM-30 (trade name)) heated to a barrel temperature of 200°C for mixing to produce granules of each resin composition.

[0752] Here, Ingeo Biopolymer 2003D (trade name, manufactured by NatureWorks LLC) was used as the polylactic acid resin (PLA).

[0753] The resin composition granules were injection molded under the following conditions to produce test pieces for evaluation.

[0754] Injection molding machine: Sumitomo Heavy Industries, Ltd., SE100DU (product name)

[0755] Barrel temperature: 200℃, mold temperature: 30℃

[0756] Test piece specifications:

[0757] Test piece A: Length 80mm × Width 10mm × Thickness 4mm

[0758] [Charpy Impact Strength]

[0759] For test piece A, a type A notch was etched according to ISO 179-1, and the Charpy impact strength was measured at 23°C. Under annealing conditions, a type A notch was etched for test piece A according to ISO 179-1, and after standing in an oven at 100°C for 3 hours, it was cooled to 23°C, and the Charpy impact strength was measured.

[0760] The higher the value, the better the impact resistance, and the better the choice.

[0761] [Table 16]

[0762]

[0763] In Example 37, the impact strength is excellent.

[0764] In Comparative Example 41, the impact strength is extremely low because it does not contain polymer particle clusters (C).

[0765] In Comparative Example 42, the impact strength was low because a polymer particle group (C) with a Z value of 60% or higher was used.

[0766] <Examples 38-39, Comparative Examples 43-44>

[0767] The compositions obtained in Manufacturing Examples 2-10 above, along with polymer particle groups (C-1), polybutylene terephthalate (PBT, NOVADURAN 5010R5, manufactured by Mitsubishi Engineering Plastics), and polycarbonate (PC, Iupilon S-2000F, manufactured by Mitsubishi Engineering Plastics, with an average viscosity molecular weight of 24,000), were blended according to the ratios in Table 17 to obtain a mixture. This mixture was fed into a devolatilization twin-screw extruder (manufactured by Ikegai Corporation, PCM-30 (trade name)) heated to a barrel temperature of 260°C for compounding to produce granules of each resin composition.

[0768] Each granule was injection molded under the following conditions to produce test pieces for evaluation.

[0769] Injection molding machine: Sumitomo Heavy Industries, Ltd., SE100DU (product name)

[0770] Barrel temperature: 260℃, mold temperature: 60℃

[0771] Test piece specifications:

[0772] Test piece A: Length 80mm × Width 10mm × Thickness 4mm

[0773] For test piece A, a type A notch was etched according to ISO 179-1, and the Charpy impact strength was measured at 23℃ and -30℃. Generally speaking, the higher the value, the better the impact resistance, and the more desirable the material.

[0774] [Melting Flowability]

[0775] Each granule was continuously injection molded 15 times under the following conditions, and its spiral flow length (SFL) was evaluated. The maximum and minimum SFL and their difference ΔSFL (maximum SFL - minimum SFL) during the 15 cycles are shown in Table 15. Higher values ​​indicate higher melt flowability and are preferred. In addition, the smaller the difference between the minimum and maximum values, the better the molding stability and are preferred.

[0776] Injection molding machine: Sumitomo Heavy Industries, Ltd., SE100DU (product name)

[0777] Barrel temperature: 300℃, mold temperature: 70℃, injection speed: 20mm / sec, injection pressure: 50MPa

[0778] [Table 17]

[0779]

[0780] Example 38 exhibits excellent impact strength, melt flowability, and molding stability.

[0781] Example 39 exhibits excellent impact strength and melt flowability. However, due to the absence of component (D), its molding stability is lower than that of Example 41.

[0782] In Comparative Example 43, the impact strength was low because no polymer particle group (C) was used.

[0783] In Comparative Example 44, the impact strength, melt flowability and molding stability were low because a polymer particle group (C) with a Z value of 60% or more was used.

[0784] <Examples 40-42, Comparative Examples 45-46>

[0785] The compositions obtained in Manufacturing Examples 2-9 to 2-10 above, polymer particle groups (C-1), polycarbonate (PC, Iupilon S-2000F, manufactured by Mitsubishi Engineering Plastics Co., Ltd., with an average viscosity molecular weight of 24,000), and polyethylene terephthalate (PET, TRN8550FF, manufactured by Teijin Co., Ltd.) were blended in the proportions shown in Table 18 to obtain a mixture. This mixture was fed into a devolatilization twin-screw extruder (manufactured by Ikegai Co., Ltd., PCM-30 (trade name)) heated to a barrel temperature of 280°C for mixing to produce granules of each resin composition.

[0786] Each granule was injection molded under the following conditions to produce test pieces for evaluation.

[0787] Injection molding machine: Sumitomo Heavy Industries, Ltd., SE100DU (product name)

[0788] Barrel temperature: 300℃, mold temperature: 70℃

[0789] Test piece specifications:

[0790] Test piece A: Length 80mm × Width 10mm × Thickness 4mm

[0791] [Charpy Impact Strength]

[0792] For test piece A, a type A notch was etched according to ISO 179-1, and the Charpy impact strength was measured at 23°C and -30°C. The higher the value, the better the impact resistance, and the better the candidate.

[0793] [Melting Flowability]

[0794] Each granule was continuously injection molded 15 times under the following conditions, and its spiral flow length (SFL) was evaluated. The maximum and minimum SFL and their difference ΔSFL (maximum SFL - minimum SFL) during the 15 cycles are shown in Table 15. Higher values ​​indicate higher melt flowability and are preferred. In addition, the smaller the difference between the minimum and maximum values, the better the molding stability and are preferred.

[0795] Injection molding machine: Sumitomo Heavy Industries, Ltd., SE100DU (product name)

[0796] Barrel temperature: 300℃, mold temperature: 70℃, injection speed: 20mm / sec, injection pressure: 50MPa

[0797] [Table 18]

[0798]

[0799] Examples 40-41 exhibit excellent impact strength, melt flowability, and molding stability.

[0800] Example 42 exhibits excellent impact strength and melt flowability. However, due to the absence of component (D), its molding stability is lower than that of Examples 40-41.

[0801] In Comparative Example 45, the impact strength and flowability were low because no polymer particle group (C) was used.

[0802] In Comparative Example 46, the impact strength, melt flowability and molding stability were low because a polymer particle group (C) with a Z value of 60% or more was used.

[0803] <Examples 43-44, Comparative Examples 47-48>

[0804] The compositions obtained in Manufacturing Examples 2-10 above, along with polymer (C-1), glass fiber-added polycarbonate resin (PCGF-2, Iupilon GSH2030R2, manufactured by Mitsubishi Engineering Plastics Co., Ltd., with 30% by mass of glass fiber added), and polyethylene terephthalate (PET, TRN8550FF, manufactured by Teijin Co., Ltd.), were blended in the proportions shown in Table 19 to obtain a mixture. This mixture was fed into a devolatilization twin-screw extruder (manufactured by Ikegai Co., Ltd., PCM-30 (trade name)) heated to a barrel temperature of 300°C for mixing to produce granules of each resin composition.

[0805] Each granule was injection molded under the following conditions to produce test pieces for evaluation.

[0806] Injection molding machine: Sumitomo Heavy Industries, Ltd., SE100DU (product name)

[0807] Barrel temperature: 300℃, mold temperature: 70℃

[0808] Test piece specifications:

[0809] Test piece A: Length 80mm × Width 10mm × Thickness 4mm

[0810] [Charpy Impact Strength]

[0811] For test piece A, a type A notch was etched according to ISO 179-1, and the Charpy impact strength was measured at 23°C and -30°C. The higher the value, the better the impact resistance, and the better the candidate.

[0812] [Melting Flowability]

[0813] Each granule was continuously injection molded 15 times under the following conditions, and its spiral flow length (SFL) was evaluated. The maximum and minimum SFL and their difference ΔSFL (maximum SFL - minimum SFL) during the 15 cycles are shown in Table 15. Higher values ​​indicate higher melt flowability and are preferred. In addition, the smaller the difference between the minimum and maximum values, the better the molding stability and are preferred.

[0814] Injection molding machine: Sumitomo Heavy Industries, Ltd., SE100DU (product name)

[0815] Barrel temperature: 300℃, mold temperature: 70℃, injection speed: 20mm / sec, injection pressure: 50MPa

[0816] [Table 19]

[0817]

[0818] Example 43 exhibits excellent impact strength, melt flowability, and molding stability.

[0819] Example 44 exhibits excellent impact strength and melt flowability. However, due to the absence of component (D), its molding stability is lower than that of Example 43.

[0820] In Comparative Example 47, the impact strength and flowability were low because no polymer particle group (C) was used.

[0821] In Comparative Example 48, the impact strength, melt flowability and molding stability were low because a polymer particle group (C) with a Z value of 60% or more was used.

Claims

1. A group of polymer particles containing a polyorganosiloxane, comprising a polymer (A) and a second vinyl polymer (B), wherein the polymer (A) comprises a polyorganosiloxane (A1) and a first vinyl polymer (A2). The percentage of the polyorganosiloxane (Al) relative to 100% by mass of the polymer particle group containing the polyorganosiloxane is more than 1% by mass and less than 30% by mass. The polyorganosiloxane (Al) has a number-average particle size of 1–100 nm, and the ratio of its mass-average particle size to its number-average particle size, Dw / Dn, is greater than 1.0 and less than 1.

7. When the cross-section of a resin sheet obtained by dispersing the polymer particle group containing the polyorganosiloxane in the resin is observed using a transmission electron microscope, and the diameter of each particle in the polymer particle group containing the polyorganosiloxane is set to L, and the maximum length of the polyorganosiloxane (Al) region is set to M, the proportion of particles satisfying the following formula (1) is less than 60%. M / L>0.1··· (1).

2. The polymer particle group containing polyorganosiloxane according to claim 1, wherein the ratio of the polyorganosiloxane (Al) to 100% by mass of the polymer particle group containing polyorganosiloxane is more than 1% by mass and less than 20% by mass.

3. The polymer particle group containing polyorganosiloxane according to claim 1 or 2, wherein the ratio of the polyorganosiloxane (Al) to 100% by mass of the polymer particle group containing polyorganosiloxane is more than 1% by mass and less than 10% by mass.

4. The polymer particle group containing polyorganosiloxane according to claim 1 or 2, wherein the number-average particle size of the polymer particle group is 10 nm or more and 150 nm or less.

5. The polymer particle group containing polyorganosiloxane according to claim 1 or 2, wherein a portion of each particle of the polymer particle group containing polyorganosiloxane is insoluble in tetrahydrofuran, and the ratio of the polymer particle group containing polyorganosiloxane that is insoluble in tetrahydrofuran to 100% by mass is more than 80% by mass and less than 100% by mass.

6. The polymer particle group containing polyorganosiloxane according to claim 1 or 2, wherein a portion of each particle of the polymer particle group containing polyorganosiloxane is soluble in tetrahydrofuran, and the weight-average molecular weight of the polymer particle group containing polyorganosiloxane soluble in tetrahydrofuran is more than 20,000 and less than 500,000.

7. The polymer particle group containing polyorganosiloxane according to claim 1 or 2, when the cross-section of the resin sheet is observed by transmission electron microscopy, the polymer (A) has an island structure in which the polyorganosiloxane (A1) is a sea component and the first vinyl polymer (A2) is an island component. In the island structure, the polyorganosiloxane (A1) region contains a plurality of the first vinyl polymer (A2) regions.

8. According to claim 1 or 2, when the cross-section of the resin sheet is observed by a transmission electron microscope, each particle of the polymer particle group containing the polyorganosiloxane has an island structure in which the polyorganosiloxane (A1) is used as the sea component, the first vinyl polymer (A2) is used as the first island component, and the second vinyl polymer (B) is used as the second island component.

9. The polymer particle group containing polyorganosiloxane according to claim 1 or 2, wherein the ratio of polymer (A) to 100% by mass of the polymer particle group containing polyorganosiloxane is 60% by mass or more and 95% by mass or less.

10. The polymer particle group containing polyorganosiloxane according to claim 1 or 2, wherein the vinyl monomer component (a2) constituting the first vinyl polymer (A2) contains a monofunctional (meth)acrylate monomer.

11. The polymer particle group containing polyorganosiloxane according to claim 1 or 2, wherein the vinyl monomer component (b) constituting the second vinyl polymer (B) contains at least one selected from the group consisting of (meth)acrylate monomers and aromatic vinyl monomers. The total ratio of the (meth)acrylate monomer and the aromatic vinyl monomer is 50% or more relative to 100% by mass of the vinyl monomer component (b).

12. The polymer particle group containing polyorganosiloxane according to claim 1 or 2, wherein the vinyl monomer component (b) constituting the second vinyl polymer (B) contains methyl methacrylate. The ratio of methyl methacrylate to the vinyl monomer component (b) is 50% by mass or more.

13. The group of polymer particles containing polyorganosiloxane according to claim 1 or 2, wherein the polymer (A) is a polymer formed by polymerizing the vinyl monomer component (a2) constituting the first vinyl polymer (A2) in the presence of a latex containing the polyorganosiloxane (A1).

14. The polymer particle group containing polyorganosiloxane according to claim 1 or 2, wherein the number-average particle size of the polyorganosiloxane (Al) is 30-60 nm.

15. A composition comprising a group of polymer particles containing a polyorganosiloxane as described in any one of claims 1 to 14, and at least one component selected from the group consisting of phosphoric acid compounds and their alkali metal salts.

16. The composition according to claim 15, wherein the alkali metal salt of the phosphoric acid compound is at least one selected from the group consisting of alkali metal salts of alkyl phosphoric acids and alkali metal salts of alkylaryl phosphoric acids.

17. The composition according to claim 15 or 16, wherein the alkali metal salt of the phosphoric acid compound is an alkali metal salt of polyoxyalkylene ether phosphoric acid.

18. The composition according to claim 15 or 16, wherein the ratio of phosphorus atoms contained in the component is 100 ppm by mass or more, relative to 100% by mass of the total group of polymer particles containing the polyorganosiloxane and at least one component selected from the group consisting of the phosphoric acid compound and its alkali metal salt.

19. A resin composition comprising a group of polymer particles containing polyorganosiloxane as described in any one of claims 1 to 14 and a thermoplastic resin.

20. A resin composition comprising the composition of any one of claims 15 to 18 and a thermoplastic resin.

21. The resin composition according to claim 19 or 20, wherein the thermoplastic resin comprises at least one selected from the group consisting of aromatic polycarbonate, polymethyl methacrylate, styrene-acrylonitrile copolymer, polyethylene terephthalate, polybutylene terephthalate, polyvinyl chloride, polyphenylene sulfide, and polyacetal.

22. A molded article comprising a group of polymer particles containing polyorganosiloxane according to any one of claims 1 to 14.

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