Polyorganosiloxane-containing polymer particle group, composition, resin composition, and molded article

Abstract

To provide a group of polyorganosiloxane-containing polymer particles that yield molded articles with excellent impact strength. [Solution] A polyorganosiloxane-containing polymer particle group according to one aspect of the present invention comprises a polymer (A) containing a polyorganosiloxane (A1) and a first vinyl polymer (A2), and a second vinyl polymer (B). When the cross-section of a resin piece obtained by dispersing the polyorganosiloxane-containing polymer particle group in a resin is observed with a transmission electron microscope, the ratio of the number of particles satisfying the following formula (1) is less than 60%, where L is the diameter of each particle in the polyorganosiloxane-containing polymer particle group and M is the maximum domain length of the polyorganosiloxane (A1). M / L>0.1 ···(1)

Description

Technical Field

[0001] The present invention relates to a group of polyorganosiloxane-containing polymer particles, a composition, a resin composition, and a molded body. This application claims priority based on Japanese Patent Application No. 2020-102397 filed in Japan on June 12, 2020, and incorporates its content herein.

Background Art

[0002] A rubber-containing polymer obtained by polymerizing a vinyl monomer with a rubbery polymer can be dispersed in a variety of resins while maintaining a predetermined rubber particle size and rubber structure, and thus is suitably used for resins that require impact strength. Generally, it is preferable to use a rubbery polymer having a low elastic modulus and a high Poisson's ratio of rubber from the viewpoint of improving impact strength. Butadiene rubber and silicone rubber have a very high Poisson's ratio of 0.5 and a low elastic modulus, and thus are suitably used as rubbery polymers. Among them, silicone rubber is less likely to cause curing or coloring by heat or ultraviolet rays and is excellent in durability compared to butadiene rubber, and thus is suitably used for applications that require maintaining mechanical properties for a long time, such as building materials and automotive parts. As the silicone rubber, polyorganosiloxane represented by polydimethylsiloxane is used.

[0003] However, polyorganosiloxane is more expensive than butadiene rubber. In addition, when a polyorganosiloxane-containing polymer is blended with a resin having a higher refractive index than the polyorganosiloxane-containing polymer (such as polycarbonate, polymethyl methacrylate, styrene-acrylonitrile copolymer, etc.) and formed into a molded body, the transparency of the molded body decreases, and there is a problem that it becomes difficult to exhibit a colored appearance, particularly a deep dark color.

[0004] Patent Document 1 describes a resin composition comprising various thermoplastic resins such as vinyl chloride resin, polycarbonate resin, and polyester resin, and a polyorganosiloxane-containing graft copolymer. In Patent Document 1, the number-average particle size of the polyorganosiloxane-containing graft copolymer is set to 5 to 80 nm, and the volume of particles larger than 100 nm is set to 10% or less of the total particle volume, thereby improving the pigment coloration properties of the resulting molded article.

[0005] Patent Document 2 describes a resin composition comprising a styrene-acrylonitrile copolymer and a polyorganosiloxane-containing graft copolymer. It also describes that the weight-average particle size of the polyorganosiloxane-containing graft copolymer should be 110 nm or less. Patent Document 3 describes a resin composition comprising a polymethyl methacrylate resin and a polyorganosiloxane-containing graft copolymer. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 6-116471 [Patent Document 2] Japanese Patent Publication No. 2009-155421 [Patent Document 3] Japanese Patent Publication No. 2000-327880 [Overview of the project] [Problems that the invention aims to solve]

[0007] However, all of the prior art methods had the problem that the impact strength of the resulting molded articles was not sufficient. The object of the present invention is to provide a group of polyorganosiloxane-containing polymer particles, compositions, and resin compositions that yield molded articles with excellent impact strength. Another object of the present invention is to provide a molded article with excellent impact strength. [Means for solving the problem]

[0008] The present invention has the following aspects. [1] A group of polyorganosiloxane-containing polymer particles comprising a polymer (A) containing a polyorganosiloxane (A1) and a first vinyl polymer (A2), and a second vinyl polymer (B), A group of polyorganosiloxane-containing polymer particles in which, when a cross-section of a resin piece obtained by dispersing the group of polyorganosiloxane-containing polymer particles in a resin is observed with a transmission electron microscope, the diameter of each particle in the group of polyorganosiloxane-containing polymer particles is L, and the maximum domain length of the polyorganosiloxane (A1) is M, the proportion of particles that satisfy the following formula (1) is less than 60%. M / L>0.1 ···(1) [2] The polyorganosiloxane-containing polymer particle group according to [1], wherein the ratio of the polyorganosiloxane (A1) to 100% by mass of the polyorganosiloxane-containing polymer particle group is 1% by mass or more and 50% by mass or less. [3] The polyorganosiloxane-containing polymer particle group according to [1] or [2], wherein the ratio of the polyorganosiloxane (A1) to 100% by mass of the polyorganosiloxane-containing polymer particle group is 1% by mass or more and 10% by mass or less. [4] A group of polyorganosiloxane-containing polymer particles from any of [1] to [3] above, having a number-average particle diameter of 10 nm or more and 150 nm or less. [5] A polyorganosiloxane-containing polymer particle group according to any of [1] to [4] above, wherein a portion of each particle of the polyorganosiloxane-containing polymer particle group is insoluble in tetrahydrofuran, and the ratio of the polyorganosiloxane-containing polymer particle group that is insoluble in tetrahydrofuran to 100% by mass of the polyorganosiloxane-containing polymer particle group is 80% by mass or more and less than 100% by mass. [6] A group of polyorganosiloxane-containing polymer particles according to any of [1] to [5] above, wherein a portion of each particle of the group of polyorganosiloxane-containing polymer particles is soluble in tetrahydrofuran, and the weight-average molecular weight of the group of polyorganosiloxane-containing polymer particles soluble in tetrahydrofuran is 20,000 or more and 500,000 or less. [7] When the cross-section of the resin piece is observed with a transmission electron microscope, the polymer (A) has a sea-island structure in which the polyorganosiloxane (A1) is the sea component and the first vinyl polymer (A2) is the island component. A group of polyorganosiloxane-containing polymer particles according to any of [1] to [6] above, wherein in the sea-island structure, the domains of the polyorganosiloxane (A1) contain multiple domains of the first vinyl polymer (A2). [8] A group of polyorganosiloxane-containing polymer particles according to any of [1] to [7] above, wherein when the cross-section of the resin piece is observed with a transmission electron microscope, each particle of the group of polyorganosiloxane-containing polymer particles has a sea-island structure in which the polyorganosiloxane (A1) is the sea component, the first vinyl polymer (A2) is the first island component, and the second vinyl polymer (B) is the second island component. [9] A group of polyorganosiloxane-containing polymer particles according to any of [1] to [8] above, wherein the ratio of polymer (A) to 100% by mass of the group of polyorganosiloxane-containing polymer particles is 60% by mass or more and 95% by mass or less.

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

[11] The vinyl monomer component (b) constituting the second vinyl polymer (B) includes at least one selected from the group consisting of (meth)acrylate monomers and aromatic vinyl monomers, A group of polyorganosiloxane-containing polymer particles from any of [1] to

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

[12] The vinyl monomer component (b) constituting the second vinyl polymer (B) contains methyl methacrylate, A group of polyorganosiloxane-containing polymer particles from any of [1] to

[11] , wherein the ratio of methyl methacrylate to 100% by mass of the vinyl monomer component (b) is 50% by mass or more.

[13] A group of polyorganosiloxane-containing polymer particles according to any of [1] to

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

[14] A composition comprising any of the polyorganosiloxane-containing polymer particle groups described in [1] to

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

[15] The composition according to

[14] , 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 acid and alkali metal salts of alkylaryl phosphoric acid.

[16] The composition according to

[14] or

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

[17] Any of the compositions described in

[14] to

[16] above, 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 of the polyorganosiloxane-containing polymer particle group and at least one component selected from the group consisting of the phosphoric acid compound and its alkali metal salt.

[18] A resin composition comprising any of the polyorganosiloxane-containing polymer particle groups described in [1] to

[13] above, and a thermoplastic resin.

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

[14] to

[17] above and a thermoplastic resin.

[20] The resin composition according to

[18] or

[19] , 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.

[21] A molded article comprising any of the polyorganosiloxane-containing polymer particle groups described in [1] to

[13] above. [Effects of the Invention]

[0009] According to the polyorganosiloxane-containing polymer particle group of the present invention, a molded article with excellent impact strength can be obtained. According to the composition of the present invention, a molded article with excellent impact strength can be obtained. According to the resin composition of the present invention, a molded article with excellent impact strength can be obtained. The molded article of the present invention exhibits excellent impact strength. [Brief explanation of the drawing]

[0010] [Figure 1] This is a transmission electron microscope (TEM) image of the polymer particle group (C-1) produced in [Example]. [Figure 2] This image shows the results of brightness image analysis performed on transmission electron microscope (TEM) images of the polymer particle group (C-1) produced in [Example]. [Figure 3] This image shows the results of brightness image analysis performed on transmission electron microscope (TEM) images of the polymer particle group (C-3) produced in [Example]. [Figure 4] This image shows the results of brightness image analysis performed on transmission electron microscope (TEM) images of the polymer particle group (C-4) produced in [Example]. [Figure 5] This image shows the results of brightness image analysis performed on transmission electron microscope (TEM) images of the polymer particle group (C-6) produced in [Example]. [Figure 6] This image shows the results of brightness image analysis performed on transmission electron microscope (TEM) images of the polymer particle group (C-7) produced in [Example]. [Figure 7]This image shows the results of brightness image analysis performed on transmission electron microscope (TEM) images of the polymer particle group (C-8) produced in [Example]. [Figure 8] This image shows the results of brightness image analysis performed on transmission electron microscope (TEM) images of the polymer particle group (C-11) produced in [Example]. [Figure 9] This image shows the results of brightness image analysis performed on transmission electron microscope (TEM) images of the polymer particle group (C-12) produced in [Example]. [Figure 10] This image shows the results of brightness image analysis performed on transmission electron microscope (TEM) images of the polymer particle group (C-13) produced in [Example]. [Figure 11] This image shows the results of brightness image analysis performed on transmission electron microscope (TEM) images of the polymer particle group (C-14) produced in [Example]. [Figure 12] This image shows the results of brightness image analysis performed on transmission electron microscope (TEM) images of the polymer particle group (C-15) produced in [Example]. [Figure 13] This image shows the results of brightness image analysis performed on transmission electron microscope (TEM) images of the polymer particle group (C-17) produced in [Example]. [Figure 14] This image shows the results of brightness image analysis performed on transmission electron microscope (TEM) images of the polymer particle group (C-18) produced in [Example]. [Figure 15] This image shows the results of brightness image analysis performed on transmission electron microscope (TEM) images of the polymer particle group (C-19) produced in [Example]. [Figure 16] This image shows the results of brightness image analysis performed on transmission electron microscope (TEM) images of the polymer particle group (C-20) produced in [Example]. [Modes for carrying out the invention]

[0011] Embodiments of the present invention will be described in detail below. In the present invention, the vinyl monomer is a compound having a polymerizable double bond. "(Meth)acrylate" is either acrylate or methacrylate. In this specification, "transmission electron microscope" will also be referred to as "TEM".

[0012] [Polyorganosiloxane-containing polymer particle group] A group of polyorganosiloxane-containing polymer particles according to one aspect of the present invention (hereinafter also referred to as "polymer particle group (C)") comprises polymer (A) and a second vinyl polymer (B) (hereinafter also referred to as "vinyl polymer (B)"). Polymer (A) comprises polyorganosiloxane (A1) and a first vinyl polymer (A2) (hereinafter also referred to as "vinyl polymer (A2)"). Polyorganosiloxane (A1), vinyl polymer (A2), polymer (A), and vinyl polymer (B) will be explained in detail later. Typically, each particle in the group of polymer particles (C) contains both polymer (A) and vinyl polymer (B).

[0013] The polymer particle group (C) is defined as a group of polymer particles in which polymer particle group (C) is dispersed in a resin. When the cross-section of the resin piece obtained by observing the polymer particle group (C) using TEM, the proportion of particles that satisfy the following formula (1) (hereinafter also referred to as the "Z value") is less than 60%, where L is the diameter (μm) of each particle in polymer particle group (C) and M is the maximum domain length (μm) of polyorganosiloxane (A1). M / L>0.1 ···(1) A Z value of less than 60% results in excellent impact strength, color appearance, and weather resistance of the molded article containing polymer particles (C). The Z value is preferably 50% or less, more preferably 30% or less, even more preferably 20% or less, and particularly preferably 10% or less. A smaller Z value is preferable, and there is no particular lower limit.

[0014] When the cross-section of the resin piece is observed by TEM, it is preferable that the polymer (A) of the polymer particle group (C) has a sea-island structure in which polyorganosiloxane (A1) is the sea component and vinyl polymer (A2) is the island component. By adopting such a sea-island structure in which polyorganosiloxane (A1) and vinyl polymer (A2) are combined, the impact strength, color appearance, and weather resistance of the molded article containing the polymer particle group (C) are further improved.

[0015] Preferably, each particle of the polymer particle group (C) has a sea-island structure in which polyorganosiloxane (A1) is the sea component, vinyl polymer (A2) is the first island component, and vinyl polymer (B) is the second island component, when the cross-section of the resin piece is observed by TEM. Having a sea-island structure in which polyorganosiloxane (A1), vinyl polymer (A2), and vinyl polymer (B) are combined results in superior impact strength and colored appearance of the molded article.

[0016] As described above, a sea-island structure composed of polyorganosiloxane (A1), vinyl polymer (A2), and vinyl polymer (B) can be formed, for example, by impregnating polymer (A) with at least a portion of the vinyl monomer component (b) constituting vinyl polymer (B) during the production of polymer particle group (C), and then polymerizing it. To impregnate polymer (A) with at least a portion of vinyl monomer component (b), for example, vinyl monomers having a solubility in water of 1.0 g / L or less at 30°C can be used for at least a portion of vinyl monomer component (b). Examples of vinyl monomers having a solubility in water of 1.0 g / L or less at 30°C include styrene, alkyl-substituted styrene, alkyl-substituted isopropenylbenzene, and 1,1-diphenylethylene, which are among the vinyl monomers described later. Methods for distinguishing between the first and second island components include, for example, TEM observation with adjusted staining conditions (specifically, stain type and staining time), elemental analysis using energy-dispersive X-ray spectroscopy, electron energy loss spectroscopy, etc. Each particle of 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) in which vinyl monomer components (b) that were not impregnated into polymer (A) are polymerized) exists on the outer surface of polymer (A) in each particle of the polymer particle group (C) as a graft polymer (a polymer covalently bonded to polymer (A)) or a free polymer (a polymer that is not covalently bonded to polymer (A) but is physically adsorbed).

[0017] Specifically, a TEM image of the cross-section of the aforementioned resin piece can be obtained by following the procedure below. (1) First, the polymer particle group (C) is placed at the tip of a polyethylene capsule, liquid uncured epoxy resin is poured over it, and it is left to stand at 25°C for 12 hours to cure, thereby obtaining a resin piece. (2) Next, the obtained resin pieces are stained with an osmium tetroxide aqueous solution (23°C, 12 hours). (3) Next, the resin pieces stained with osmium tetroxide aqueous solution are stained with ruthenium tetroxide aqueous solution (23°C, 5 hours). (4) Next, sections are cut from the resin piece after staining with ruthenium tetroxide aqueous solution using a microtome and collected on a copper grid with a support film. The thickness of the sections should be 50 nm. (5) Next, a randomly selected 0.5 μm of the surface of the section (cross-section of the resin piece) is examined by TEM. 2 Acquire an image (TEM image) within the above range. The image acquisition magnification will be 200,000x.

[0018] As shown in Figure 1, the resulting TEM image shows a continuous phase consisting of the epoxy resin cured material (hereinafter also referred to as the "resin region"), and dispersed within the resin region, the regions of each individual particle of the polymer particle group (C) (hereinafter also referred to as the "particle region") are observed. Furthermore, as shown in Figure 1, the TEM image shows that within the particle region, the polyorganosiloxane (A1) region (hereinafter also referred to as the "polyorganosiloxane (A1) domain") is identified with bright contrast, while the vinyl polymer (A2) or vinyl polymer (B) region (hereinafter also referred to as the "vinyl polymer domain") is identified with dark contrast. The "TEM image" in Figure 1 is a TEM image obtained of the polymer particle group (C-1) produced in the example described later.

[0019] From the obtained TEM image, as shown in Figure 2, the particle region, polyorganosiloxane (A1) domain, and vinyl polymer domain can be extracted using image analysis software (e.g., ImageJ). Specifically, the contrast of particle regions in the TEM image is extracted by line profile measurement. In line profile measurement, the maximum Ferret diameter in a particle region is defined as the major axis, and the minimum Ferret diameter as the minor axis. A line is drawn passing through the intersection of these two axes (hereinafter also referred to as the "center point"), cutting across the particle diameter. If the maximum and minimum Ferret diameters are the same, multiple lines representing the same Ferret diameter can be arbitrarily determined, and the center point can be found from their intersections. Furthermore, the lines are drawn so that neither end of the line touches an adjacent particle region. The length of the drawn line is defined as the diameter L of the particle region. In addition, lines can be drawn arbitrarily at locations that satisfy the above requirements, but it is preferable to draw multiple lines in a single particle region and adopt the line that shows the largest ratio (hereinafter also referred to as the "M / L value") between the diameter L of the particle region and the maximum domain length M of the polyorganosiloxane (A1), which is determined by the method described later, as the line profile for that particle region. When drawing multiple lines, it is preferable to first draw an arbitrary first line, then draw a second line such that the angle it makes with the first line at its midpoint (where the angle is defined as an angle of 90° or less) is between 30° and 60°, and then draw a third line perpendicular to the second line at its midpoint. By evaluating these three lines, it is preferable to select the line that shows the largest M / L value. However, if it is not possible to draw multiple lines that satisfy the above requirements, the M / L value obtained from evaluating fewer than three lines may be adopted.

[0020] In this case, particle regions that fall under the following categories cannot be distinguished as a single particle and are therefore not selected as particle regions for line profile measurement. (i) Particle regions that are cut off at the edge of the image. (ii) Particles whose size is less than 80% of the average particle diameter. (iii) A particle region in which there are adjacent particle regions in three or more directions, and the boundaries of each particle region are unclear. All remaining particle regions visible in the image are measured, and line profiles are measured for a total of 50 or more particle regions. If it is not possible to measure 50 or more particle regions that do not fall under (i) to (iii) above in a single TEM image, measurements are taken from multiple TEM images acquired at different observation locations and the results are summed up. The average particle diameter in (ii) above is the average value of the equivalent circle diameter of the particle region observed in the image.

[0021] Next, the distance from one end to the other of a line drawn in the particle region is plotted on the horizontal axis (X-axis), and the contrast (Gray Value) on the line is plotted on the vertical axis (Y-axis) as the Y value. The maximum Y value and 75% of the maximum value (denoted as the YA value) within a single particle region are then determined. Areas showing a Y value greater than the YA value are defined as HGV areas. Here, since a brighter (lighter) color indicates a larger Y value, and polyorganosiloxane (A1) domains are observed as light contrast and vinyl polymer domains as dark contrast, HGV areas can be identified as polyorganosiloxane (A1) domains. Among the HGV regions, the one with the longest continuity length within a single particle region is defined as the maximum domain of polyorganosiloxane (A1) within that particle region, and the continuity length of that HGV region is defined as the maximum domain length M. Here, the continuity length of the HGV region refers to the distance between the intersection points of the Gray Value and the line drawn using the YA value (shown as a dashed line in Figure 2) at peaks where the Gray Value exceeds the YA value.

[0022] Of the particle regions for which line profile measurements were performed, the number of particle regions that satisfy equation (1) above is defined as Z1, and the number of particle regions that do not satisfy equation (1) above is defined as Z2. The Z value is then calculated using the following equation (2). Z-value = {Z1 / (Z1+Z2)} × 100 ... (2)

[0023] In Figure 2, "TEM image" is an image obtained by line profile measurement using ImageJ on a TEM image of polymer (C-1) produced in the example described later. In Figure 2, "Analysis Example" shows an example of graphing and analyzing the results of line profile measurement performed using ImageJ for polymer (C-1). In the "Analysis Examples," the line length (diameter L) is converted to 1 for easy comparison of particle regions with different particle sizes. The same applies to Figures 3-16 described later.

[0024] In the aforementioned sea-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 even better. The lower limit of the average diameter of the vinyl polymer domains is not particularly limited, but is, for example, 2 nm.

[0025] In the aforementioned sea-island structure, from the viewpoint of the impact strength of the molded article, it is preferable that multiple vinyl polymer domains are included in the polyorganosiloxane (A1) domain. Furthermore, the average diameter of the vinyl polymer domains is preferably 50 nm or less, and more preferably 30 nm or less. The lower limit of the average diameter of the vinyl polymer (A2) domains is not particularly limited, but is, for example, 2 nm.

[0026] The vinyl polymer domain may consist solely of the vinyl polymer (A2) domain, or it may consist of both the vinyl polymer (A2) domain and the vinyl polymer (B) domain. If the vinyl polymer domain consists only of the vinyl polymer (A2) domain, the average diameter of the vinyl polymer domain is the average diameter of the vinyl polymer (A2) domain.

[0027] The average diameter of vinyl polymer domains can be determined by various methods, but for example, it can be determined from the TEM image described above. Specifically, it can be determined by following the procedure below. First, a TEM image is obtained using the procedure described above. Next, from the obtained TEM image, the particle region, polyorganosiloxane (A1) domain, and vinyl polymer domain are extracted using image analysis software (for example, product name "Image-Pro(registered trademark) Plus," manufactured by Nippon Roper Co., Ltd.). Specifically, after flattening the brightness unevenness of the background and removing noise from the TEM image, binarization is performed using the maximum brightness boundary where the surrounding resin region is not selected as the boundary, thereby allowing the particle region, polyorganosiloxane (A1) domain, and vinyl polymer domain to be extracted, respectively. Of the identified particle regions, 30% or more and 100 or more are selected, prioritizing those with the largest area, and used for measurement. The ratio of selected particle regions refers to the ratio of the number of selected particle regions to the total number of particle regions with an equivalent circle diameter of 10 nm or more that are identified in the image. For each selected particle region to be measured, vinyl polymer domains with an equivalent circle diameter of 10 nm or more are selected from among the vinyl polymer domains present in that region, and the average of the equivalent circle diameters of these vinyl polymer domains is taken as the average diameter. The average of the average diameters obtained for all particle regions to be measured can then be taken as the average diameter of the vinyl polymer domains.

[0028] The ratio of polyorganosiloxane (A1) to 100% by mass of polymer particles (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, while 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 colored appearance of the molded article is better.

[0029] The ratio of polymer (A) to 100% by mass of polymer particle group (C) is preferably 60% by mass or more, more preferably 65% ​​by mass or more, while preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less. If the polymer (A) content is above the lower limit, the impact strength of the molded article is better, and if it is below the upper limit, the dispersibility of polymer particle group (C) in thermoplastic resin is better, and the appearance of the resulting molded article is better. The ratio of polymer (A) to 100% by mass of polymer particle group (C) may be, for example, 60-95% by mass, 60-90% by mass, 65-90% by mass, or 65-85% by mass.

[0030] The ratio of vinyl polymer (B) to 100% by mass of polymer particle group (C) is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, while it is preferably 40% by mass or less, and more preferably 35% by mass or less. If the content of vinyl polymer (B) is above the lower limit, the dispersibility of polymer particle group (C) in thermoplastic resin is better, and the appearance of the resulting molded article is better. If it is below the upper limit, the impact strength of the molded article is better. The ratio of vinyl polymer (B) to 100% by mass of polymer particle group (C) may be, for example, 5 to 40% by mass, 10 to 40% by mass, 10 to 35% by mass, or 15 to 35% by mass.

[0031] Typically, a portion of each particle in the polymer particle group (C) is insoluble in tetrahydrofuran (hereinafter also referred to as "THF"). In other words, a portion of each particle in the polymer particle group (C) is soluble in THF. 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 portion," and the portion that is soluble in THF will be referred to as the "THF-soluble portion."

[0032] The ratio of THF-insoluble matter to 100% by mass of polymer particle group (C) is preferably 80% by mass or more, more preferably 85% by mass or more, even more preferably 90% by mass or more, and particularly preferably 93% by mass or more. On the other hand, it is preferably less than 100% by mass, and more preferably 99% by mass or less. If the ratio of THF-insoluble matter is above the lower limit, the dispersibility of polymer particle group (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 matter 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. The ratio of THF-insoluble matter to 100% by mass of polymer particles (C) may be 80% by mass or more and less than 100% by mass, 85% by mass or more and less than 100% by mass, 90% by mass or more and 99% by mass or less, or 93% by mass or more and 99% by mass or less.

[0033] THF-insoluble content is measured by performing the following steps (1-1) to (1-5). (1-1) Add 0.5 g of the sample (polymer particle group (C)) to 50 mL (44.5 g) of THF to prepare a mixed solution, let it stand at 25°C for 8 hours, then stir with a stirrer for 30 minutes to dissolve the THF-soluble components. (1-2) The mixed solution is placed in a centrifuge tube whose mass has been measured, and the THF-insoluble portion and the THF-soluble portion are separated by centrifugation using a centrifuge (16000 rpm, 4 hours). (1-3) After removing the supernatant, fresh THF is added and stirred, and then centrifuged again in the same manner as in (1-2) above to wash away any THF-insoluble components. (1-4) After repeating (1-3) twice, remove the supernatant. Immerse the centrifuge tube containing the remaining THF-insoluble matter in a hot water bath (80°C, 8 hours) to volatilize the THF, then vacuum dry at 65°C for 6 hours to obtain a dried sample (THF-insoluble matter adhering to the centrifuge tube). (1-5) Measure the mass of the obtained dried sample (THF insoluble matter + centrifuge tube), and calculate the ratio of THF insoluble matter w using the following formula. ais Calculate the percentage (%). wais =(w c1 -w as ) / wt×100 wt: Mass of the polymer particle group (C) used for measurement. w as : Mass of the centrifuge tube, w c1 : Mass of THF-insoluble matter (mass including centrifuge tube).

[0034] From the viewpoint of keeping the ratio of THF-insoluble matter in the polymer particle group (C) within the aforementioned range, it is preferable that the vinyl polymer (A2) is sufficiently crosslinked and that the polyorganosiloxane (A1) and the vinyl polymer (A2) are covalently bonded. Furthermore, it is preferable that the vinyl polymer (B) is covalently bonded to polymer (A).

[0035] The weight-average molecular weight of the THF-soluble portion of polymer particle group (C) is preferably 20,000 or more, more preferably 50,000 or more, while 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. If the weight-average molecular weight of the THF-soluble component is between 20,000 and 500,000, the dispersibility of the polymer particle group (C) in the thermoplastic resin is excellent, resulting in superior impact strength and appearance of the resulting molded article. In particular, if the weight-average molecular weight of the THF-soluble component is between 50,000 and 150,000, the dispersibility of the polymer particle group (C) in the thermoplastic resin is especially good, resulting in superior impact strength and appearance of the resulting molded article under a wide range of molding conditions, including low levels of kneading. The weight-average molecular weight of the THF-soluble portion of polymer particle group (C) may be between 20,000 and 500,000, between 20,000 and 350,000, between 50,000 and 200,000, or between 50,000 and 150,000.

[0036] The weight-average molecular weight of THF-soluble components is measured by performing the following steps (2-1) to (2-3). (2-1) From the liquid containing THF-soluble components obtained by measuring the ratio of THF-insoluble components as described above, THF is removed by vacuum distillation using a rotary evaporator to obtain THF-soluble components. (2-2) The THF-soluble components obtained in (2-1) above are dissolved again in THF to a sample concentration of 0.1 to 0.3% by mass to obtain a THF solution of the THF-soluble components. (2-3) The THF solution containing the THF soluble components obtained in (2-2) above is subjected to gel permeation chromatography (GPC) and the weight-average molecular weight (Mw) is determined from a calibration curve using standard polystyrene. The GPC measurement conditions are as described in the examples below.

[0037] The weight-average molecular weight of the THF-soluble component can be adjusted by the amount of initiator and reducing agent, polymerization temperature, and use of chain transfer agent when polymerizing the vinyl monomer component (b) that constitutes the vinyl polymer (B). For example, increasing the amount of initiator and reducing agent or raising the polymerization temperature to increase radical generation, or accelerating the chain transfer reaction by adding a chain transfer agent or increasing the amount added, will decrease the weight-average molecular weight of the THF-soluble component.

[0038] The number-average particle diameter of the polymer particle group (C) is preferably 10 nm or more, more preferably 30 nm or more, even more preferably 50 nm or more, and particularly preferably 70 nm or more. On the other hand, it is preferably 800 nm or less, more preferably 500 nm or less, even more preferably 200 nm or less, particularly preferably 150 nm or less, especially preferably 130 nm or less, and most preferably 100 nm or less. If the number-average particle diameter is above the lower limit, the impact strength of the molded article is better, and if it is below the upper limit, the colored appearance of the molded article is better. The number-average particle diameter of the polymer particle group (C) may be, for example, 10 to 800 nm, 30 to 500 nm, 50 to 200 nm, 50 to 150 nm, 70 to 130 nm, or 70 to 100 nm.

[0039] The method for measuring the number-average particle diameter of a group of polymer particles (C) is not particularly limited, but it can be measured by the following method, for example. The latex of polymer particle group (C) was diluted to a concentration of approximately 3% with deionized water as a sample. The particle size distribution based on the number of particles was measured using a capillary particle size analyzer (MATEC CHDF2000 particle size analyzer, USA), and the median diameter was defined as the number-average particle size.

[0040] Particle size distribution can be measured under the following standard conditions recommended by MATEC. Cartridge: Dedicated capillary cartridge for particle separation (product name: C-202) Carrier fluid: Dedicated carrier fluid (product name: 2XGR500) pH of the carrier solution: Neutral, Carrier fluid flow rate: 1.4 mL / min Carrier fluid pressure: approximately 4,000 psi (2,600 kPa), Measurement temperature: 35℃, Sample volume used: 0.1 mL. Furthermore, as standard particle size materials, 12 types of monodisperse polystyrene with known particle sizes, manufactured by DUKE Corporation in the United States, are used, with particle sizes ranging from 40 to 800 nm.

[0041] The number-average particle size of the polymer particle group (C) can be adjusted, for example, by the amount of emulsifier used when the polymer particle group (C) is produced by emulsion polymerization.

[0042] (Polyorganosiloxane (A1)) Polyorganosiloxane (A1) is a polymer containing organosiloxane units. Polyorganosiloxane (A1) can be obtained by polymerizing an organosiloxane mixture containing an organosiloxane. The organosiloxane mixture may further contain components used as needed. Components that may be used as needed include at least one selected from the group consisting of siloxane crosslinking agents, siloxane cross-linking agents, and siloxane oligomers having terminal sealing groups.

[0043] Examples of organosiloxanes include linear organosiloxanes, alkoxysilane compounds, and cyclic organosiloxanes, all of which can be used. Among these, alkoxysilane compounds and cyclic organosiloxanes are preferred, and cyclic organosiloxanes are particularly preferred due to their high polymerization stability and high polymerization rate.

[0044] Preferred alkoxysilane compounds are bifunctional alkoxysilane compounds, such as dimethyldimethoxysilane, dimethyldiethoxysilane, diethoxydiethylsilane, dipropoxydimethylsilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, and methylphenyldiethoxysilane. These can be used individually or in combination of two or more.

[0045] As cyclic organosiloxanes, those with 3 to 7 membered rings are preferred, such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, and octaphenylcyclotetrasiloxane. These can be used individually or in combination of two or more. Among these, octamethylcyclotetrasiloxane is preferred because it allows for easy control of the particle size distribution.

[0046] As the organosiloxane, it is preferable to select at least one from the group consisting of cyclic dimethylsiloxanes and bifunctional dialkylsilane compounds, in order to obtain a group of polymer particles (C) that can increase the impact strength of the molded article.

[0047] Cyclic dimethylsiloxane is a cyclic siloxane having two methyl groups on a silicon atom, and examples thereof include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane and the like. These can be used alone or in combination of two or more.

[0048] The bifunctional dialkylsilane compound is a silane compound having two alkoxy groups and two alkyl groups on a silicon atom, and examples thereof include dimethyldimethoxysilane, dimethyldiethoxysilane, diethoxydiethylsilane, dipropoxydimethylsilane and the like. These can be used alone or in combination of two or more.

[0049] As the siloxane-based crosslinking agent, those having a siloxy group are preferred. Examples of the siloxane-based crosslinking agent include trifunctional or tetrafunctional silane-based crosslinking agents such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetrabutoxysilane and the like. Among them, a tetrafunctional crosslinking agent is preferred, and tetraethoxysilane is more preferred.

[0050] The ratio of the siloxane-based crosslinking agent to 100% by mass of the organosiloxane mixture is preferably 10% by mass or less, more preferably 5% by mass or less, and may be 0% by mass. When the content of the siloxane-based crosslinking agent is 10% by mass or less, polymer particle groups (C) with better impact strength of the molded body can be obtained.

[0051] The siloxane-based crosslinking agent has a siloxy group (-Si-O-) and a functional group capable of polymerizing with a vinyl monomer. Examples of the siloxane-based crosslinking agent include siloxanes represented by the following formula (I). R-Si(R 1 ) n (OR 2 ) (3-n) (I) In formula (I), R 1R represents a methyl group, ethyl group, propyl group, or phenyl group. 2 n represents an organic group such as a hydrocarbon group, preferably a methyl group, ethyl group, propyl group, or phenyl group. n represents 0, 1, or 2. R represents a functional group represented by any of the following formulas (I-1) to (I-4). CH2=C(R 3 )-COO-(CH2) p - (I-1) CH2=C(R 4 )-C6H4- (I-2) CH2=CH- (I-3) HS-(CH2) p - (I-4) In these formulas, R 3 and R 4 Each of these independently represents either a hydrogen atom or a methyl group, and p represents an integer from 1 to 6.

[0052] Examples of functional groups represented by formula (I-1) include methacryloyloxyalkyl groups. Examples of siloxanes having this group include: β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, γ-methacryloyloxypropyldiethoxymethylsilane, δ-methacryloyloxybutyldiethoxymethylsilane, etc.

[0053] Examples of functional groups represented by formula (I-2) include the vinylphenyl group. Examples of siloxanes having this group include vinylphenylethyldimethoxysilane. Examples of siloxanes having a functional group represented by formula (I-3) include vinyltrimethoxysilane and vinyltriethoxysilane.

[0054] Examples of functional groups represented by formula (I-4) include mercaptoalkyl groups. Examples of siloxanes having this group include: γ-mercaptopropyl dimethoxymethylsilane, γ-mercaptopropyl methoxydimethylsilane, γ-mercaptopropyl diethoxymethylsilane, γ-mercaptopropyl ethoxydimethylsilane, γ-mercaptopropyl trimethoxysilane, etc.

[0055] Siloxane cross-agents can be used individually or in combination of two or more. As a siloxane-based cross-agent, 3-methacryloxypropylmethyldimethoxysilane is preferred because it readily forms a sea-island structure when combined with polyorganosiloxane (A1) and vinyl polymer (A2).

[0056] 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, while 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 graft cross-linking agent is within the range of the above upper and lower limits, sufficient covalent bonds can be formed between the polyorganosiloxane (A1) and the vinyl polymer (A2), and a group of polymer particles (C) with good impact strength can be obtained. The ratio of the siloxane cross-agent to 100% by mass of the organosiloxane mixture may be, for example, 0.05 to 20% by mass, 0.1 to 10% by mass, or 0.5 to 5% by mass.

[0057] The number-average particle diameter of polyorganosiloxane (A1) is preferably 1 nm or more, more preferably 10 nm or more, even more preferably 30 nm or more, while it is preferably 500 nm or less, more preferably 300 nm or less, even more preferably 150 nm or less, particularly preferably 100 nm or less, especially preferably 80 nm or less, and most preferably 60 nm or less. If the number-average particle diameter of polyorganosiloxane (A1) is within the range of the above upper and lower limits, it is easy to adjust the number-average particle diameter of the polymer particle group (C) to within the above preferred upper and lower limits. The number-average particle size of polyorganosiloxane (A1) may be, for example, 1 to 500 nm, 1 to 300 nm, 10 to 150 nm, 10 to 100 nm, 30 to 80 nm, or 30 to 60 nm.

[0058] The ratio of the mass-average particle diameter (nm) to the number-average particle diameter (nm) of the polyorganosiloxane (A1) (hereinafter also referred to as "Dw / Dn") is preferably 1.0 or greater, and preferably 1.7. If Dw / Dn is within the range of the upper and lower limits, the colorability of the resin composition containing the polymer particle group (C) and the thermoplastic resin is better, and the colored appearance of the molded article using the resin composition is better.

[0059] The method for measuring the number-average particle size (Dn) of polyorganosiloxane (A1) is the same as the method for measuring the number-average particle size of polyorganosiloxane (A1) described above. The method for measuring the mass-average particle size (Dw) of polyorganosiloxane (A1) is the same as the method for measuring the number-average particle size of polyorganosiloxane (A1) described above, except that a mass-based particle size distribution is measured instead of a number-based particle size distribution. Specifically, a sample of polyorganosiloxane (A1) latex diluted to a concentration of approximately 3% with deionized water is used, and the mass-based particle size distribution is measured using a capillary particle size analyzer (MATEC CHDF2000 particle size analyzer, USA), with the median diameter being taken as the mass-average particle size.

[0060] <Method for producing polyorganosiloxane (A1)> There are no particular restrictions on the method for producing polyorganosiloxane (A1), and for example, the following methods can be employed. First, an organosiloxane mixture containing an organosiloxane, optionally a siloxane-based crosslinking agent, optionally a siloxane-based cross-linking agent, and optionally a siloxane oligomer having a terminal-binding group 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, and then the acid catalyst is neutralized with an alkaline substance to obtain a polyorganosiloxane latex. In the following description of the manufacturing method, we will explain the case where an "organosiloxane mixture" is used as the raw material for polymerization, but the same manufacturing process can also be applied when using "organosiloxane".

[0061] In this manufacturing method, methods for preparing the emulsion include using a homomixer that atomizes particles by shear force due to high-speed rotation, and mixing by high-speed stirring using a homogenizer that atomizes particles by jet force from a high-pressure generator. Among these, the method using a homogenizer is preferred because it narrows the particle size distribution of the polyorganosiloxane latex.

[0062] Methods for mixing the acid catalyst during polymerization include (1) adding the acid catalyst together with the organosiloxane mixture, emulsifier, and water and mixing them together; (2) adding the acid catalyst aqueous solution together to the organosiloxane mixture emulsion; and (3) dropping the organosiloxane mixture emulsion into a high-temperature acid catalyst aqueous solution at a constant rate and mixing them. Among these, the method of dropping the organosiloxane mixture emulsion into a high-temperature acid catalyst aqueous solution at a constant rate is preferred because it allows for easy control of the particle size of the polyorganosiloxane.

[0063] The polymerization temperature is preferably 50°C or higher, and more preferably 70°C or higher. The upper limit of the polymerization temperature is, for example, 100°C. The polymerization time is usually 2 hours or more, preferably 5 hours or more, when polymerizing an emulsion of organosiloxane mixtures by dropping it dropwise into a high-temperature acid catalyst aqueous solution at a constant rate.

[0064] Furthermore, since crosslinking reactions between silanols proceed at temperatures below 30°C, in order to increase the crosslinking density of polyorganosiloxanes, the latex produced can be polymerized at a high temperature of 50°C or higher and then held at a temperature below 30°C for 5 to 100 hours.

[0065] The polymerization reaction of organosiloxane mixtures can be terminated by neutralizing the reaction system containing latex with an alkaline substance such as sodium hydroxide, potassium hydroxide, or aqueous ammonia solution to a pH of 6 to 8.

[0066] The emulsifier used in the above manufacturing method is not particularly limited as long as it can emulsify the organosiloxane mixture, but anionic or nonionic emulsifiers are preferred. Examples of anionic emulsifiers include sodium alkylbenzenesulfonate, sodium alkyldiphenyl ether disulfonate, sodium alkyl sulfate, sodium polyoxyethylene alkyl sulfate, and sodium polyoxyethylene nonylphenyl ether sulfate. Examples of nonionic emulsifiers include: polyoxyethylene alkyl ethers, polyoxyethylene alkylene alkyl ethers, polyoxyethylene distyleninated phenyl ethers, polyoxyethylene tripenzylphenyl ethers, and polyoxyethylene polyoxypropylene glycol. These emulsifiers can be used individually or in combination of two or more.

[0067] The amount of emulsifier used is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, per 100 parts by mass of the organosiloxane mixture, while preferably 20 parts by mass or less, and more preferably 10 parts by mass or less. By adjusting the amount of emulsifier used, it is possible to adjust the particle size of the polyorganosiloxane latex to a desired value. If the amount of emulsifier used is above the lower limit, the emulsification stability of the organosiloxane mixture emulsion can be improved. If the amount of emulsifier used is below the upper limit, the heat discoloration resistance and surface appearance of the molded article are better.

[0068] Acid catalysts used in the polymerization of organosiloxane mixtures include sulfonic acids such as aliphatic sulfonic acid, aliphatic-substituted benzenesulfonic acid, and aliphatic-substituted naphthalenesulfonic acid, as well as mineral 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 mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid can narrow the particle size distribution of polyorganosiloxane latex and further suppress the occurrence of defects caused by emulsifier components in polyorganosiloxane latex (such as reduced thermal decomposition resistance of molded products and poor appearance).

[0069] The amount of acid catalyst used is preferably 0.005 parts by mass or more and 40 parts by mass or less per 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 to discoloration and surface appearance of the molded article are better.

[0070] Furthermore, since the amount of acid catalyst used is a factor that determines the particle size of polyorganosiloxane (A1), it is more preferable to use an amount of acid catalyst of 1 to 30 parts by mass per 100 parts by mass of organosiloxane (A1) in order to obtain polyorganosiloxane (A1) with the particle size described later.

[0071] The polyorganosiloxane latex obtained by the above method may contain an emulsifier as needed to improve its mechanical stability. Anionic or nonionic emulsifiers similar to those exemplified above are preferred as emulsifiers.

[0072] (Vinyl polymer (A2)) Vinyl polymer (A2) is a polymer obtained by polymerizing vinyl monomer components (a2), and consists of units based on vinyl monomers. The vinyl monomer component (a2) that constitutes the vinyl polymer (A2) consists of one or more vinyl monomers.

[0073] From the viewpoint of the impact strength of the molded article, the vinyl monomer component (a2) preferably contains a monofunctional (meth)acrylate monomer (hereinafter also referred to as "monomer (a2-1)"). The vinyl monomer component (a2) may further include, in addition to monomer (a2-1), at least one selected from the group consisting of other monofunctional monomers different from monomer (a2-1) that can copolymerize with monomer (a2-1) (hereinafter also referred to as "monomer (a2-2)") and polyfunctional monomers that can copolymerize with monomer (a2-1) (hereinafter also referred to as "monomer (a2-3)"). From the viewpoint of impact strength of the molded article and keeping the ratio of THF-insoluble matter in the polymer particle group (C) within the aforementioned range, the vinyl monomer component (a2) preferably contains monomer (a2-1) and monomer (a2-3).

[0074] 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, i-butyl methacrylate, t-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, tridecyl methacrylate, and stearyl methacrylate. In particular, since the impact strength of the molded article is improved, 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. These monomers (a2-1) can be used individually or in combination of two or more.

[0075] Examples of monomers (a2-2) include aromatic vinyl monomers such as styrene and α-methylstyrene, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, and various vinyl monomers such as (meth)acrylic group-modified silicones. These monomers (a2-2) can be used individually or in combination of two or more.

[0076] Examples of monomers (a2-3) include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butylene glycol diacrylate, 1,6-hexanediol diacrylate, divinylbenzene, polyfunctional (meth)acrylic group modified silicone, allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, and the like. In particular, since the impact strength of the molded article is better, the monomer (a2-3) is preferably at least one selected from the group consisting of allyl methacrylate, triallyl cyanurate, and triallyl isocyanurate, with allyl methacrylate being more preferred. These monomers (a2-3) can be used individually or in combination of two or more.

[0077] From the viewpoint of impact strength of the molded article, the ratio of monomer (a2-1) to 100% by mass of vinyl monomer component (a2) is preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. The ratio of monomer (a2-1) to vinyl monomer component (a2) may be 100% by mass, but it is preferable to be 99.9% by mass or less.

[0078] The ratio of monomer (a2-2) to 100% by mass of vinyl monomer component (a2) 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 even be 0% by mass, from the viewpoint of the impact strength of the molded article.

[0079] The ratio of monomer (a2-3) to vinyl monomer component (a2) (100% by mass) is preferably 0.1% by mass or more and 4% by mass or less. From the viewpoint of further increasing 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. From the viewpoint of further enhancing the colored appearance of the molded article, the ratio of monomer (a2-3) to 100% by mass of vinyl monomer component (a2) 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. 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, from the viewpoint of balancing melt fluidity during molding with the colored appearance and impact strength of the molded article.

[0080] (Polymer (A)) Polymer (A) comprises a polyorganosiloxane (A1) and a vinyl polymer (A2). In polymer (A), the mass ratio of polyorganosiloxane (A1) to vinyl polymer (A2) (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, from the viewpoint of the impact strength of the molded article.

[0081] <Method for producing polymer (A)> The method for producing polymer (A) is not particularly limited, but a method of polymerizing the vinyl monomer component (a2) constituting the vinyl polymer (A2) in the presence of a latex containing polyorganosiloxane (A1) is preferred because it results in superior impact strength of the molded article.

[0082] The method for polymerizing the vinyl monomer component (a2) in the presence of a latex containing polyorganosiloxane (A1) is not particularly limited and includes: (i) a method of polymerizing by dropwise adding the vinyl monomer component (a2) to a latex containing polyorganosiloxane (A1); (ii) a method of adding a portion of the vinyl monomer component (a2) to a latex containing polyorganosiloxane (A1) under conditions where polymerization has not started, impregnating the polyorganosiloxane (A1) particles, then starting polymerization, and then adding the remainder of the vinyl monomer component (a2) dropwise or all at once for polymerization; and (iii) a method of adding the entire amount of the vinyl monomer component (a2) to a latex containing polyorganosiloxane (A1) under conditions where polymerization has not started, impregnating the polyorganosiloxane (A1) particles, and then polymerizing.

[0083] As for the method of producing polymer (A), among the above, a method is preferred in which the impact strength of the molded article is superior, and the entire amount of vinyl monomer component (a2) is added to latex containing polyorganosiloxane (A1) under conditions in which polymerization has not started, impregnating the particles of polyorganosiloxane (A1), and then polymerization is performed.

[0084] As a method for producing polymer (A), a method having the following steps i to iv is particularly preferred. According to this method, polymer (A) can be easily obtained that has a sea-island structure in which polyorganosiloxane (A1) is the sea component and vinyl polymer (A2) is the island component, and which has multiple domains of vinyl polymer (A2) in the domain of polyorganosiloxane (A1), and which can achieve polymer particle group (C) having a Z value of less than 60%.

[0085] Process i: Polyorganosiloxane (A1) latex is produced under arbitrary conditions. Polyorganosiloxane (A1) latex can be produced by the method described above. In this case, polyorganosiloxane (A1) preferably consists of an organosiloxane and a siloxane-based cross-agent.

[0086] Step ii: In step i, the entire amount of the vinyl monomer component (a2) and a radical polymerization initiator are added to the polyorganosiloxane (A1) latex obtained, under conditions that prevent polymerization of the vinyl monomer component (a2) from starting, thereby impregnating the polyorganosiloxane (A1) particles. At this time, by adding the entire amount of vinyl monomer component (a2), the impact strength of the molded product is further improved.

[0087] If the vinyl monomer component (a2) contains multiple types of vinyl monomers, for example, if it contains monomer (a2-1) and at least one 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) or / and monomer (a2-3) may be added simultaneously, or monomer (a2-1) and monomer (a2-2) or / and monomer (a2-3) may be added separately. When the vinyl monomer component (a2) contains monomer (a2-3), it is preferable to mix it with monomer (a2-1) and / or monomer (a2-2) before adding it, from the viewpoint of obtaining an appropriate crosslinking structure.

[0088] Radical polymerization initiators are not particularly limited, but examples include azo compounds, peroxides, and dihalogens. These can be used individually or in combination of two or more.

[0089] Examples of azo compounds include the following: Oil-soluble azo initiators such as 2,2'-azobisisobutyronitrile, dimethyl-2,2'-azobis(2-methylpropionate), 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(2-butyronitrile); water-soluble azo initiators such as 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis[N-(2-carboxymethyl)-2-methylpropionamidine]hydrate, 2,2'-azobis-(N,N'-dimethylene isobutylamidine) dihydrochloride, and 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride. These can be used individually or in combination of two or more.

[0090] When using an azo compound as a radical polymerization initiator, the amount of azo compound used is preferably 0.01% by mass or more, with respect to 100% by mass of the total monomers to be polymerized; 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 above upper and lower limits, it is possible to suppress an excessively high polymerization rate and facilitate the construction of the aforementioned sea-island structure.

[0091] Examples of peroxides include the following: Inorganic peroxides such as hydrogen peroxide, potassium persulfate, and ammonium persulfate; organic peroxides such as diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, succinic acid peroxide, t-butyl peroxyneodecanoate, t-butyl peroxyneoheptanoate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, and t-butyl peroxy-2-ethylhexanoate. These can be used individually or in combination of two or more. In particular, it is preferable that the 10-hour half-life temperature is between 25°C and 105°C, as this facilitates handling during emulsion polymerization.

[0092] When using a peroxide as a radical polymerization initiator, the amount of peroxide used is preferably 0.01% by mass or more, with respect to 100% by mass of the total monomers to be polymerized; more preferably 1% by mass or less; more preferably 0.5% by mass or less; and even more preferably 0.2% by mass or less. By keeping the amount of peroxide used within the range of the above upper and lower limits, it is possible to suppress an excessively high polymerization rate and facilitate the construction of the aforementioned sea-island structure.

[0093] Peroxides are preferred as radical polymerization initiators because they allow for easy control of the polymerization rate and result in superior impact strength of the molded articles.

[0094] When using peroxides as radical polymerization initiators, reducing agents can be used in combination to promote the decomposition of the peroxides.

[0095] Examples of reducing agents include sulfur compounds such as sulfites, hydrogen sulfites, alkali metal bisulfites, acetone bisulfites, alkali metal disulfites, metabisulfites and their salts; organic sulfur compounds such as thiosulfates, sulfinic acid, hydroxylalkylsulfinic acid, hydroxylmethylsulfinic acid and 2-hydroxy-2-sulfinic acid, formazinesulfinic acid, propylsulfinic acid, isopropylsulfinic acid and phenylsulfinic acid; reducing nitrogen compounds such as formaldehyde sulfoxylates and their salts, hydroxylamines, hydroxylamine hydrosulfate, hydroxylammonium salts, polyamines and dimethylaniline; reducing sugars such as sorbose, fructose, glucose, lactose and dextrose; and enediols such as ascorbic acid and isoascorbic acid. Examples of "salts" include sodium ions, potassium ions, ammonium ions and zinc ions.

[0096] Furthermore, sulfates, nitrates, acetates, carbonates, and chlorides of transition metals located between groups 3 and 11 of the periodic table are also useful 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).

[0097] As a reducing agent, at least one selected from the group consisting of sodium formaldehyde sulfoxylate, L(+)-tartaric acid, sodium disulfite, sodium isoascorbate, and L-ascorbic acid and ferrous sulfate is preferred because it is readily available industrially and provides superior heat resistance, discoloration, and surface appearance of the molded article.

[0098] 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 equivalent or less, even more preferably 0.6 molar equivalents or less, and may even be 0 molar equivalents. By keeping the amount of reducing agent below the above upper limit, it is possible to suppress an excessively high polymerization rate and facilitate the construction of the aforementioned sea-island structure.

[0099] When using transition metal salts as reducing agents, chelating agents can be used in combination to enhance their reactivity. As chelating agents, compounds containing two or more electron-donating atoms capable of forming a coordinate bond with the target transition metal atom can be used. Examples include ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, nitrilotriacetic acid, citric acid, tartaric acid, gluconic acid, 5-sulfosalicylic acid, ethylenediamine, diethylenetriamine, triethylenetetramine, triaminotriethylamine, triethanolamine, N-hydroxyethylethylenediamine, sodium oxalate, and their metal salts. Among these, ethylenediaminetetraacetic acid and its metal salts are preferred due to their excellent polymerization stability.

[0100] From the standpoint of controlling polymerization reactivity, the amount of chelating agent used is preferably 0.5 molar equivalents or more, more preferably 1.0 equivalent or more, relative to the reducing agent, while preferably 5.0 molar equivalents or less, and more preferably 2.5 molar equivalents or less.

[0101] In step ii, if necessary, an aqueous medium may be added to the polyorganosiloxane (A1) latex. Examples of aqueous media include water and mixed media of water and organic solvents. The organic solvent in the mixed media can be any solvent that is miscible with water, such as methanol and ethanol.

[0102] In step ii, an emulsifier may be added to the polyorganosiloxane (A1) latex as needed. The emulsifier is not particularly limited, and emulsifiers similar to those used in the production of the polyorganosiloxane (A1) described above can be used. Among these, anionic or nonionic emulsifiers are preferred. Alternatively, the emulsifier may be omitted in step ii, and polymerization may be carried out using only the emulsifier contained in the polyorganosiloxane (A1) latex.

[0103] A chain transfer agent may be used when polymerizing the vinyl monomer component (a2). Examples of chain transfer agents include mercaptans such as n-dodecyl mercaptan, t-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 dimer. These chain transfer agents may be used individually or in combination of two or more.

[0104] The amount of chain transfer agent used is preferably 1.0% by mass or less, and may be 0% by mass, relative to 100% by mass of the vinyl monomer component (a2). By using 1.0% by mass or less of the chain transfer agent, the decrease in the THF-insoluble content ratio of the polymer particle group (C) is suppressed, resulting in superior impact strength of the molded article.

[0105] Step iii: In step ii, the latex of polyorganosiloxane (A1) to which the vinyl monomer component (a2) and radical polymerization initiator have been added is subjected to the polymerization of the vinyl monomer component (a2) under conditions that satisfy the following formula (a). T 10 >(T in +10) ... (A) Here, T 10 This represents the 10-hour half-life temperature of the radical polymerization initiator used, and T in This represents the temperature at which polymerization of the vinyl monomer component (a2) is initiated. When using a combination of multiple radical polymerization initiators, the T value of the radical polymerization initiator exhibiting the lowest 10-hour half-life temperature is used. 10 Use the value.

[0106] The condition that equation (A) is satisfied, in other words, the temperature T at which polymerization of the vinyl monomer component (a2) begins. in (Hereinafter, polymerization temperature (T in ) Let ) be the 10-hour half-life temperature T of the radical polymerization initiator. 10 By lowering the temperature by more than 10°C, the polymerization rate can be suppressed, making it easier to construct a sea-island structure composed of the polyorganosiloxane (A1) and vinyl polymer (A2), and thus obtaining a group of polymer particles (C) that can produce a molded article with better impact strength. Polymerization temperature (T in ) is the 10-hour half-life temperature T of the radical polymerization initiator. 10 It is preferable that the temperature is at least 15°C lower, and more preferably at least 20°C lower. Polymerization temperature (T in The lower limit of the radical polymerization initiator is not particularly limited, but from the viewpoint of the stability of polymerization initiation, the 10-hour half-life temperature T 10 It is preferable that the temperature is not more than 50°C lower than that. Polymerization time is determined by the polymerization temperature (T in It varies depending on the circumstances, but for example, it is between 0.1 and 30 hours.

[0107] 10-hour half-life temperature T 10 This is the temperature at which 50 mol% of the radical polymerization initiator used thermally decomposes in 10 hours. For example, by substituting the conversion rate X = 50 [%] of the radical polymerization initiator, time t = 36000 [s] (= 10 hours), gas constant R = 8.314 [J / Kmol], frequency factor A, and activation energy E from literature or calculated values ​​into the following equations (a) and (c), the 10-hour half-life temperature T of the radical polymerization initiator can be obtained. 10 It is possible to calculate the following: 10-hour half-life temperature T 10 For this purpose, literature values ​​may be used.

[0108] X = 100 × exp(-kdt) ... (i) kd = A × exp(-E / RT) ... (c) (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) For example, the 10-hour half-life temperature of potassium persulfate is 67°C, while the 10-hour half-life temperature of t-butyl hydroperoxide (trade name Perbutyl H69, manufactured by Nippon Oil & Fats Co., Ltd.) is 167°C.

[0109] Step iv: In the polymerization behavior after polymerization is initiated in step iii, the highest temperature in the system reached by the polymerization of the vinyl monomer component (a2) is T. p (°C), the temperature inside the system is T in After reaching +1°C, T in +{(T p -T in S is the time required to reach ) / 3}(℃ p (seconds) (Hereinafter, polymerization rate (S p When ) and ) are assumed, polymerization is carried out so as to satisfy the following formula (E). S p ≥80 ···(E)

[0110] Polymerization rate (S p By setting the polymerization rate (S) to 80 seconds or more, it becomes easier to construct a sea-island structure composed of the polyorganosiloxane (A1) and vinyl polymer (A2) described above, and a group of polymer particles (C) can be obtained that can improve the impact strength of the resulting molded article. p ) is more preferably 100 seconds or more, even more preferably 120 seconds or more, and particularly preferably 150 seconds or more. Polymerization rate (S p ) The type, amount, and polymerization initiation temperature T of the radical polymerization initiator are specified. in In addition, it can be adjusted by a heat removal system during polymerization.

[0111] (Vinyl polymer (B)) Vinyl polymer (B) is a polymer obtained by polymerizing vinyl monomer component (b), and consists of units based on vinyl monomers. The vinyl monomer component (b) that constitutes the vinyl polymer (B) consists of one or more vinyl monomers. The vinyl monomer constituting the vinyl monomer component (b) is not particularly limited, but examples include various vinyl monomers such as (meth)acrylate monomers, aromatic vinyl monomers, and vinyl cyanide monomers.

[0112] Examples of (meth)acrylate monomers include alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and i-butyl methacrylate; and alkyl acrylates such as methyl acrylate, ethyl acrylate, and n-butyl acrylate. Examples of aromatic vinyl monomers include styrene, alkyl-substituted styrenes (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 isopropenylbenzenes (isopropenylbenzene (α-methylstyrene), isopropenyltoluene, isopropenylethylbenzene, isopropenylpropylbenzene, isopropenylbutylbenzene, isopropenylpentylbenzene, isopropenylhexylbenzene, isopropenyloctylbenzene, etc.), and 1,1-diphenylethylene. Among these, styrene and α-methylstyrene are preferred because they can suppress the generation of cullet. Examples of vinyl cyanide monomers include acrylonitrile and methacrylonitrile. These can be used individually or in combination of two or more types.

[0113] The vinyl monomer component (b) preferably contains at least one selected from the group consisting of (meth)acrylate monomers and aromatic vinyl monomers, in terms of having superior weather resistance of the molded article. The ratio of the total (meth)acrylate monomer and aromatic vinyl monomer to 100% by mass of vinyl monomer component (b) is preferably 50% by mass or more.

[0114] Among (meth)acrylate monomers and aromatic vinyl monomers, the vinyl monomer component (b) more preferably contains either methyl methacrylate or styrene, or both, because these exhibit particularly excellent weather resistance in the molded product. The ratio of the total amount of methyl methacrylate and styrene to 100% by mass of vinyl monomer component (b) is preferably 50% by mass or more.

[0115] The vinyl monomer component (b) preferably contains a (meth)acrylate monomer in that it provides better dispersibility of the polymer particle group (C) in thermoplastic resins and better weather resistance of the molded article. The ratio of (meth)acrylate monomer to 100% by mass of vinyl monomer component (b) is preferably 50% by mass or more.

[0116] Among vinyl monomer components (b), methyl methacrylate is more preferable because it exhibits particularly excellent dispersibility of the polymer particle group (C) in thermoplastic resins and weather resistance of the molded article. It is more preferable that the ratio of methyl methacrylate to 100% by mass of vinyl monomer component (b) is 50% by mass or more.

[0117] 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, while preferably 105°C or lower. If the Tg of the vinyl polymer (B) is above the lower limit, the powder properties (powder fluidity and particle size) of the polymer particle group (C) will be good. The Tg of vinyl polymer (B) can be adjusted by the type and ratio of vinyl monomers that make up vinyl monomer component (b).

[0118] The Tg of vinyl polymer (B) can be determined by FOX's formula. In this case, the Tg of the vinyl monomer homopolymer constituting vinyl monomer component (b) can be found in, for example, the values ​​listed in "POLYMER HANDBOOK" (Wiley Interscience, 1999). The Tg of vinyl monomer homopolymers not listed in this literature can be calculated using Bicerano's method, "Prediction of Polymer Properties" (Marcel Dekker, 2002).

[0119] (Method for producing polymer particle group (C)) The polymer particle group (C) can be produced, for example, by polymerizing (graft polymerization) a vinyl monomer component (b) in the presence of polymer (A). This yields a polymer in which some or all of the vinyl polymer (B) is grafted onto polymer (A).

[0120] A preferred method for producing the polymer particle group (C) is to add a vinyl monomer component (b) to the latex of the polymer (A) and polymerize the vinyl monomer component (b) in the latex. As described above, the latex of polymer (A) is preferably produced by polymerizing a vinyl monomer component (a2) in the presence of a latex containing polyorganosiloxane (A1).

[0121] The polymerization temperature (T) of the vinyl monomer component (b) (hereinafter referred to as "polymerization temperature (T) b It is also written as "). ) is not particularly limited and conventional conditions can be applied, for example, a temperature of 45-95°C and a polymerization time of 0.1-10 hours.

[0122] The method for adding the vinyl monomer component (b) to the latex of polymer (A) is not particularly limited, but dropwise addition is preferred because it suppresses the generation of cullet and improves the grafting rate of polymer (A) and vinyl monomer component (b). In this case, the entire amount of vinyl monomer component (b) may be added dropwise, or it may be added dropwise in multiple steps with holding periods in between during which vinyl monomer component (b) is not added. When the vinyl monomer component (b) consists of multiple types of vinyl monomers, the method for continuously adding the entire amount of vinyl monomer component (b) dropwise is not particularly limited, and examples include a method of continuously adding a mixture of the same composition, or a method of adding while continuously changing the composition, such as in power feed polymerization. When the vinyl monomer component (b) consists of multiple types of vinyl monomers, methods for adding it dropwise in multiple steps with holding time in between include a method of adding a mixture of the same composition in multiple steps, or a method of adding each component individually and / or a mixture of different compositions in multiple steps.

[0123] When the vinyl monomer component (b) includes a (meth)acrylate monomer, an aromatic vinyl monomer, and a vinyl cyanide monomer, it is preferable to polymerize the (meth)acrylate monomer first, and then polymerize the aromatic vinyl monomer and the vinyl cyanide monomer. Polymerization by this method results in good powder properties (powder fluidity and particle size) of the polymer particle group (C) obtained by performing a powder recovery step after polymerization.

[0124] The vinyl monomer component (b) can form a graft polymer with polymer (A) by chemically bonding with units based on siloxane-based cross-agents contained in polyorganosiloxane (A1) and / or units based on monomers (a2-3) contained in vinyl polymer (A2).

[0125] To improve the efficiency of this grafting, polyfunctional monomers such as ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butylene glycol diacrylate, 1,6-hexanediol diacrylate, divinylbenzene, polyfunctional (meth)acrylic group-modified silicone, allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, etc., can be polymerized beforehand before adding vinyl monomer component (b).

[0126] The emulsifier used when polymerizing the vinyl monomer component (b) is not particularly limited, and the same emulsifier used in the production of polyorganosiloxane (A1) and / or vinyl polymer (A2) can be used, but anionic or nonionic emulsifiers are preferred. Alternatively, polymerization of the vinyl monomer component (b) may be carried out using only the emulsifier contained in the vinyl polymer (A2) latex without adding any additional emulsifier.

[0127] The total amount of emulsifier used in the production of polyorganosiloxane (A1), vinyl polymer (A2), and vinyl monomer component (b) is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and more preferably 10 parts by mass or less, and more preferably 5 parts by mass or less, based on 100 parts by mass of the total amount of monomers forming the polymer particle group (C). The particle size of the latex of the polymer particle group (C) can be adjusted to a desired value by controlling the total amount of emulsifier. If the total amount of emulsifier is above the lower limit, the stability of the latex of polyorganosiloxane (A1), the latex of polymer (A), and the latex of polymer (C) can be sufficiently enhanced. If the total amount of emulsifier is below the upper limit, the amount of emulsifier remaining in the powder of the polymer particle group (C) can be sufficiently reduced, and the deterioration of the thermal decomposition resistance and surface appearance of the molded article using the resin composition containing the polymer particle group (C) and thermoplastic resin can be suppressed.

[0128] When polymerizing the vinyl monomer component (b), a chain transfer agent may be used to adjust the THF-soluble content, adjust the molecular weight, etc. Examples of chain transfer agents include mercaptans such as n-dodecyl mercaptan, t-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 dimer. These chain transfer agents may be used individually or in combination of two or more.

[0129] The amount of chain transfer agent used is preferably 2.0% by mass or less, and may be 0% by mass, relative to 100% by mass of the vinyl monomer component (b). By using 2.0% by mass or less of the chain transfer agent, the decrease in the proportion of THF-insoluble components in the polymer particle group (C) is suppressed, resulting in superior impact strength of the molded article.

[0130] After polymerizing the vinyl monomer component (b), the polymer particle group (C) may be recovered as a powder from the latex of the obtained polymer particle group (C). When recovering the polymer particle group (C) as a powder, a direct drying method such as spray drying or a coagulation method can be used. In the coagulation method, the washing step after coagulation can reduce the amount of polymerization aid residues contained in the resulting powder, such as emulsifiers and their coagulation salts, initiators, etc., used during polymerization. On the other hand, in the direct drying method, the additives added during polymerization can be largely retained in the resulting powder. These powder recovery methods can be appropriately selected to achieve a desirable residue state when the polymer particle group (C) is added to a thermoplastic resin.

[0131] The spray drying method involves spraying latex polymer particle group (C) in the form of fine droplets into a dryer and drying them with a heating gas. Methods for generating the fine droplets include, for example, a rotating disc type, a pressure nozzle type, a two-fluid nozzle type, and a 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 for drying is preferably 200°C or lower, and more preferably 120-180°C. Two or more graft copolymer latexes manufactured separately can also be spray dried together. Furthermore, to improve powder properties such as blocking and bulk density during spray drying, optional components such as silica can be added to the latex polymer particle group (C) before spray drying.

[0132] The coagulation method is a method for separating, recovering, and drying polymer particle group (C) latex by coagulation. First, polymer (C) latex is added to hot water in which a coagulant has been dissolved, and the polymer particle group (C) is separated by salting out and coagulation. Next, the separated moist polymer particle group (C) is dehydrated or otherwise processed to recover the polymer particle group (C) with reduced moisture content. The recovered polymer particle group (C) is dried using a press dewatering machine or a hot air dryer.

[0133] Examples of coagulants include inorganic salts such as aluminum chloride, aluminum sulfate, sodium sulfate, magnesium sulfate, sodium nitrate, and calcium acetate, as well as acids such as sulfuric acid, with calcium acetate being particularly preferred. These coagulants can be used individually or in combination of two or more.

[0134] The above-mentioned coagulant is usually used as an aqueous solution. From the viewpoint of stably coagulating and recovering the polymer particle group (C), the concentration of the aqueous coagulant 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 group (C) and preventing deterioration of the molded appearance of the molded article, the concentration of the aqueous coagulant solution is preferably 20% by mass or less, and particularly preferably 15% by mass or less. The amount of the coagulant aqueous solution is not particularly limited, but it is preferably 10 parts by mass or more and 500 parts by mass or less per 100 parts by mass of latex of polymer particle group (C).

[0135] The method for bringing the latex polymer particle group (C) into contact with the aqueous solution of the coagulant is not particularly limited, but the following methods are commonly used. (1) A method of continuously adding latex to an aqueous solution of a coagulant while stirring it, and holding it for a certain period of time. (2) A method of continuously injecting an aqueous solution of a coagulant and latex into a container equipped with a stirrer at a constant ratio, bringing them into contact, and continuously withdrawing a mixture containing the coagulated polymer and water from the container. The temperature at which the latex is brought into contact with the aqueous solution of the coagulant is not particularly limited, but it is preferably between 30°C and 100°C. The contact time is not particularly limited.

[0136] The coagulated polymer particle group (C) is washed with water in an amount of 1 to 100 times its mass and filtered. The filtered, wet polymer particle group (C) is dried using a fluidized bed dryer or a press dewatering machine. The drying temperature and drying time can be appropriately determined depending on the polymer particle group (C) obtained. Furthermore, it is also possible to send the polymer particle group (C) discharged from the press dewatering machine or extruder directly to an extruder or molding machine that manufactures the resin composition, and mix it with a thermoplastic resin to obtain a molded product, without recovering it.

[0137] [Composition] A composition according to one aspect of the present invention (hereinafter also referred to as "this composition") comprises a group of polymer particles (C) and at least one component selected from the group consisting of phosphoric acid compounds and alkali metal salts thereof (hereinafter also referred to as "component (D)"). Component (D) plasticizes the resin composition containing polymer particles (C), improving the fluidity of the resin composition during molding. It also suppresses the decrease in molecular weight of the resin composition, thereby improving molding stability.

[0138] Examples of phosphoric acid compounds in component (D) include alkyl phosphates such as polyoxyalkylene alkyl ether phosphate and alkylaryl phosphates such as polyoxyalkylene alkylphenyl ether phosphate. In polyoxyalkylene alkylphenyl ether phosphate and polyoxyalkylene alkyl ether phosphate, examples of polyoxyalkylene groups include polyoxyethylene groups, with polyoxyethylene groups 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. Examples of alkali metal salts include sodium salts and potassium salts.

[0139] As for component (D), alkali metal salts of phosphorus compounds are preferred, and alkali metal salts of alkyl phosphates and alkylaryl phosphates are more preferred, from the viewpoint of the ease with which the phosphorus atom content can be adjusted as described later. Among these, alkali metal salts of polyoxyalkylene alkylphenyl ether phosphate and alkali metal salts of polyoxyalkylene alkyl ether phosphate are preferred, and alkali metal salts of polyoxyalkylene alkyl ether phosphate are more preferred, from the viewpoint of the fluidity of the resin composition during molding and molding stability. As the alkali metal salt of polyoxyalkylene alkylphenyl ether phosphate, an alkali metal salt of polyoxyethylene alkylphenyl ether phosphate is preferred. As the alkali metal salt of polyoxyalkylene alkyl ether phosphate, an alkali metal salt of polyoxyethylene alkyl ether phosphate is preferred. Among these, alkali metal salts of polyoxyethylene alkyl ether phosphate are preferred. These compounds can be used individually or in combination of two or more.

[0140] The content of component (D) in this composition is determined by considering the ratio of phosphorus atoms contained in component (D) to 100% by mass of the total of polymer particle group (C) and component (D) (hereinafter also referred to as "phosphorus content"). From the viewpoint of the fluidity 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, even more 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, but for example, it is 2000 ppm by mass or less, preferably 1500 ppm by mass or less.

[0141] This composition may further contain other emulsifiers besides component (D). There are no particular restrictions on the other emulsifiers; for example, the same emulsifiers used in the production of polymer particle group (C) can be used. The total ratio of polymer particle group (C) to component (D) relative to 100% by mass of this composition is preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 98% by mass or more.

[0142] A preferred embodiment of the composition comprises a group of polymer particles (C) and an emulsifier, wherein at least a portion of the emulsifier is recovered in powder form from latex, and is an alkali metal salt of the phosphoric acid compound. Such compositions can be produced, for example, by adding an alkali metal salt of a phosphoric acid compound to the latex of the polymer particle group (C) (which may contain other emulsifiers) and recovering the powder, 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. Methods for powder recovery include those similar to the method for recovering the polymer particle group (C) as powder from the latex of the polymer particle group (C) described above. However, this composition is not limited to this. For example, it may be a mixture of polymer particle group (C) powder and component (D).

[0143] [Resin composition] A resin composition according to 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 "thermoplastic resin (E)"). The resin composition may contain the composition itself instead of the polymer particle group (C). In this case, the resin composition contains the polymer particle group (C), component (D), and thermoplastic resin (E).

[0144] The thermoplastic resin (E) is not particularly limited and includes, for example, 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, and the like.

[0145] As the engineering plastic, various known thermoplastic engineering plastics can be used without particular limitation. 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, polyether ketone, polyether ether ketone, polysulfone, polyethersulfone, polyamide-imide, polyether-imide, and polyacetal.

[0146] Furthermore, special styrene-based resins such as heat-resistant ABS and heat-resistant acrylic resins, which require high heat resistance and melt-fluidity, can also be exemplified as engineering plastics in this invention. Among these, aromatic polycarbonates and polybutylene terephthalate are more preferable when greater strength development is required. Examples of aromatic polycarbonates include 4,4'-dioxydiarylalkane polycarbonates such as 4,4'-dihydroxydiphenyl-2,2-propane (i.e., bisphenol A) polycarbonates.

[0147] Examples of olefin resins include high-density polyethylene, medium-density polyethylene, low-density polyethylene, copolymers of ethylene and other α-olefins; polypropylene, copolymers of propylene and other α-olefins; polybutene, poly-4-methylpentene-1, and the like.

[0148] Examples of thermoplastic elastomers include styrene-based elastomers, urethane-based elastomers, polyolefin-based elastomers, polyamide-based elastomers, fluorine-based elastomers, chlorinated PE-based elastomers, and acrylic elastomers.

[0149] 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-butylene-styrene copolymer (partially hydrogenated styrene-butadiene-styrene copolymer: SBBS), partially hydrogenated styrene-isoprene-styrene copolymer, and partially hydrogenated styrene-isoprene-butadiene-styrene copolymer. "-" indicates that monomers forming units linked by "-" are copolymerized, and "·" indicates that the material exists after random modification by hydrogenation or other means after copolymerization.

[0150] Examples of urethane-based elastomers include reaction products of polymeric diols, organic diisocyanates, and chain extenders. Examples of polymeric diols include polyester diols, polyether diols, polyester ether diols, polycarbonate diols, and polyester polycarbonate diols. Examples of organic diisocyanates include 4,4'-diphenylmethane diisocyanate, toluene diisocyanate, p-phenylenediisocyanate, xylylene 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. Examples of chain extenders include ethylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 2-methyl-1,3-propanediol, 1,6-hexanediol, neopentyl glycol, 1,9-nonanediol, cyclohexanediol, and 1,4-bis(β-hydroxyethoxy)benzene.

[0151] 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-acrylic acid ester copolymer.

[0152] 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.

[0153] Polyester resins are polymers of polybasic acids and polyhydric alcohols, and are not particularly limited, provided they are thermoplastic. Examples of polybasic acids include terephthalic acid, naphthaldicarboxylic acid, cyclohexyldicarboxylic acid, and their esters. Examples of polyhydric alcohols include ethylene glycol, propylene glycol, butanediol, pentanediol, neopentyl glycol, hexanediol, octanediol, decanediol, cyclohexanedimethanol, hydroquinone, bisphenol A, 2,2-bis(4-hydroxyethoxyphenyl)propane, 1,4-dimethyloltetrabromobenzene, and tetrabromobisphenol A bis(2-hydroxyethyl) ether (TBA-EO). The polyester resin may be a homopolymer, copolymer, or a blend of two or more of these. As the polyester resin, commercially available products such as "PETG" manufactured by Eastman Chemical may be used.

[0154] Examples of biodegradable resins include microbial polymers, chemically synthesized polymers, and natural product polymers. Examples of microbial polymers include biopolyesters such as polyhydroxybutyrate / variate (PHB / V), bacterial cellulose, and microbial polysaccharides (pullulan, curdlan, etc.). 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.). Examples of natural polymers include chitosan, cellulose, starch, and cellulose acetate.

[0155] Examples of halogenated resins include vinyl chloride homopolymers, copolymers containing 80% or more by mass of vinyl chloride, and polyvinyl chloride resins. Besides vinyl chloride, other components of the copolymer include monovinylidene compounds such as ethylene, vinyl acetate, methyl methacrylate, and butyl acrylate. These compounds may be contained in the copolymer in a total amount of 20% or less by mass. Examples of halogenated resins include vinyl chloride resin, as well as fluorinated polymers, brominated polymers, and iodized polymers.

[0156] Examples of acrylic resins include copolymers obtained by polymerizing methyl methacrylate with copolymerizable vinyl monomers. Examples of copolymerizable vinyl monomers include alkyl acrylates such as methyl acrylate, ethyl acrylate, i-propyl 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 vinyltoluene.

[0157] Polymer alloys of engineering plastics such as polyphenylene ether, polycarbonate, polyethylene terephthalate and polybutylene terephthalate, polyamide resins such as syndiotactic polystyrene, 6-nylon and 6,6-nylon, polyarylate, polyphenylene sulfide, polyether ketone, polyether ether ketone, polysulfone, polyethersulfone, polyamide-imide, polyether-imide, and polyacetal, and other thermoplastic resins are also included in the scope of thermoplastic resin (E) in the present invention.

[0158] These thermoplastic resins (E) can be used individually or in combination of two or more types. The thermoplastic resin (E) is preferably made up of 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, due to its industrial availability and superior balance of impact strength and colorability of the molded article. It is more preferably made up of at least one selected from the group consisting of polymethyl methacrylate and styrene-acrylonitrile copolymer.

[0159] In addition to the above, this resin composition may contain various well-known additives, as long as they do not impair the objectives of the present invention. Examples of additives include flame retardants (phosphorus-based, bromine-based, silicone-based, organometallic salt-based, etc.), drip inhibitors (e.g., fluorinated polyolefins, silicones, and aramid fibers), lubricants (e.g., long-chain fatty acid metal salts such as magnesium stearate), release agents (e.g., pentaerythritol tetrastearate), nucleating agents, antistatic agents, stabilizers (e.g., phenolic stabilizers, sulfur-based stabilizers, phosphorus-based stabilizers, ultraviolet absorbers, amine-based light stabilizers, etc.), fillers (titanium dioxide, talc, mica, kaolin, calcium carbonate, glass flakes, etc.), plasticizers, reinforcing agents (e.g., glass fibers, carbon fibers, etc.), dyes, and pigments.

[0160] Phenolic stabilizers are stabilizers having a phenolic hydroxyl group, and among them, hindered phenolic antioxidants are preferably used in which one or two carbon atoms adjacent to the carbon atom of the aromatic ring to which the phenolic hydroxyl group is attached are substituted with substituents having four or more carbon atoms. In this case, the substituents having four or more carbon atoms may be bonded to the carbon atom of the aromatic ring by a carbon-carbon bond, or they may be bonded via atoms other than carbon.

[0161] Examples of phenolic stabilizers include non-hindered phenolic antioxidants such as p-cyclohexylphenol, 3-t-butyl-4-methoxyphenol, 4,4'-isopropylidenediphenol, and 1,1-bis(4-hydroxyphenyl)cyclohexane, as well as 2-t-butyl-4-methoxyphenol, 2,6-di-t-butyl-p-cresol, 2,4,6-tri-t-butylphenol, 4-hydroxymethyl-2,6-di-t-butylphenol, styrene-phenol, 2,5-di-t-butylhydroquinone, and oc Tadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, triethylene glycol bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(6 1,1,3-Tris[2-methyl-4-hydroxy-5-t-butylphenyl]butane, 1,3,5-Tris[3,5-di-t-butylphenyl]butane, 1,3,5-Tris[3,5-di-t-butylphenyl]butane, 1,3,5-Tris[3,5-di-t-butylphenyl]butane, 1,3,5-Tris[2-methyl-4-hydroxy-5-t-butylphenyl]butane, 1,3,5-Tris[3,5-di-t Examples of hindered phenol antioxidants include [butyl-4-hydroxybenzyl]benzene, tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, tris[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate, 4,4'-thiobis(3-methyl-6-t-butylphenol), 2,2'-thiobis(4-methyl-6-t-butylphenol), 4,4'-thiobis(2-methyl-6-t-butylphenol), and thiobis(β-naphthol).In particular, hindered phenol antioxidants are suitable for use as radical trapping agents because they readily become stable radicals themselves. These phenol stabilizers can be used alone or in combination of two or more.

[0162] The content of the phenolic stabilizer per 100% by mass of the resin composition is preferably 0.001% by mass or more, more preferably 0.003% by mass or more, while preferably 2% by mass or less, and more preferably 1% by mass or less. If the content of the phenolic stabilizer is above the lower limit, the antioxidant effect is superior, and if it is below the upper limit, the thermal oxidative stability of the resin composition and resin decomposition during melt kneading can be further suppressed.

[0163] Sulfur-based stabilizers are stabilizers that do not have phenolic hydroxyl groups but contain sulfur atoms. They act as decomposers for hydroperoxides generated during the degradation of thermoplastic resins, thereby improving the heat aging resistance of resin compositions and enhancing the retention of color, tensile strength, elongation, etc. Sulfur-based stabilizers can be used alone, but long-term thermal stability can be further improved by using them in combination with the aforementioned phenol-based stabilizers.

[0164] Examples of sulfur-based stabilizers include didodecylthiodipropionate, ditetradecylthiodipropionate, dioctadecylthiodipropionate, pentaerythritol tetrakis(3-dodecylthiopropionate), thiobis(N-phenyl-β-naphthylamine), 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, nickel dibutyldithiocarbamate, nickel isopropyl xanthate, and trilauryl trithiophosphite. In particular, thioether-based stabilizers having a thioether structure can be suitably used because they accept oxygen from oxidized substances and reduce them. These sulfur-based stabilizers can be used alone or in combination of two or more.

[0165] The content of the sulfur-based stabilizer per 100% by mass of the resin composition is preferably 0.001% by mass or more, more preferably 0.003% by mass or more, while preferably 2% by mass or less, and more preferably 1% by mass or less. If the content of the sulfur-based stabilizer is above the lower limit, the thermal stabilization effect is superior, and if it is below the upper limit, the decomposition of the resin composition during melt kneading can be further suppressed.

[0166] Phosphorus-based stabilizers are stabilizers containing a phosphorus atom and are phosphite ester compounds having a P(OR)3 structure. Here, R is an alkyl group, alkylene group, aryl group, arylene group, etc., and the three Rs may be the same or different, and two Rs may form a ring structure. Furthermore, a single molecule may have multiple P(OR)3 structures. Phosphorus-based stabilizers act as decomposers of hydroperoxides generated by the degradation of thermoplastic resins, thereby improving the heat aging resistance of resin compositions and enhancing the retention of color tone, tensile strength, elongation, etc. Phosphorus-based stabilizers can be used alone, but when used in combination with the phenol-based stabilizers mentioned above, long-term thermal stability can be particularly improved, and yellowing caused by the phenol-based stabilizers can be suppressed.

[0167] Examples of phosphite ester compounds include triaryl phosphites (triphenyl phosphite, tricresyl phosphite, trixylenyl phosphite, trinaphthyl phosphite, etc.), diarylalkyl phosphites (diphenyl isooctyl phosphite, diphenyldecyl phosphite, and other diaryl C1-18 alkyl phosphites), aryl dialkyl phosphites (aryl C1-18 dialkyl phosphites such as phenyl diisooctyl phosphite, etc.), and trialkyl phosphites (trimethyl phosphite). Triethyl phosphite, tri-n-butyl phosphite, triisooctyl phosphite, tridecyl phosphite, triisodecyl phosphite, and other tri-C1-18 alkyl phosphites, dialkyl phosphites (di-C1-18 alkyl phosphites such as dilauryl phosphite), phosphites containing alkylaryl units [tris(2,4-t-butylphenyl) phosphite, tris(nonylphenyl) phosphite, tris(dinonylphenyl) phosphite, dinonylphenyl-o-biphenyl phosphite, etc.] Tris(C1-18 alkyl-aryl) phosphite, 2,2-methylenebis(4,6-di-t-butylphenyl)octyl phosphite, etc., aliphatic carboxylic acid phosphites (C1-18 aliphatic carboxylic acid phosphite such as tristearyl phosphite, etc.), phosphites containing alkylene oxide units (polydipropylene glycol nonylphenyl phosphate, tetraphenyldipropylene glycol phosphite, etc.), phosphites containing cyclic neopentane units [cyclic neopentane tetraylbis(octa Decyl phosphites, cyclic neopentanetetraylbis(2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis(2,6-di-t-butyl-4-methylphenyl) phosphite, etc., diphosphites (diisodecylpentaerythritol diphosphite, didodecylpentaerythritol diphosphite, 4,4'-isopropylidenediphenyl didodecyl diphosphite, etc.), triphosphites [heptasysdipropylene glycol triphosphite, hexa-tridecyl-1,1,Examples include 3-tri(3-t-butyl-6-methyl-4-oxyphenyl)-3-methylpropanetriphosphite, etc. These phosphite ester compounds can be used alone or in combination of two or more.

[0168] In particular, when using resins such as polycarbonate resin, polyester resin, polyamide resin, and polyacetal resin as thermoplastic resins (E), which contain carbonate ester bonds, ester bonds, amide bonds, or acetal bonds in their polymer constituent units, it is preferable to use phosphorus-based stabilizers with high hydrolysis resistance, from the viewpoint of suppressing the decrease in the moisture-resistant thermal decomposition properties of these thermoplastic resins. In particular, phosphite ester compounds in which the number of phosphorus atoms in one molecule is 1 and the number of carbon atoms in each ester part (if multiple ester parts form a ring, the total number of carbon atoms in the region between the ester bonds is defined as the number of carbon atoms in each part) is 8 or more, or phosphite ester compounds in which multiple phosphorus atoms are present in one molecule and the number of carbon atoms in the ester parts between each phosphorus element is 8 or more are preferred. Examples include tri-C6-18 alkyl phosphite (triisodecyl phosphite, etc.), phosphites containing branched C3-6 alkyl groups (t-butyl group, etc.) [tris(2,4-t-butylphenyl) phosphite, 2,2-methylenebis(4,6-di-t-butylphenyl)octyl phosphite, etc.], and tetraalkyl(C12-15)-4,4'-isopropylidenediphenyl diphosphite.

[0169] The content of the phosphorus-based stabilizer per 100% by mass of the resin composition is preferably 0.001% by mass or more, more preferably 0.003% by mass or more, while preferably 2% by mass or less, and more preferably 1% by mass or less. If the content of the phosphorus-based stabilizer is above the lower limit, the thermal stabilization effect is superior, and if it is below the upper limit, the decomposition of the resin composition during melt kneading and the decrease in moisture-resistant thermal decomposition can be further suppressed.

[0170] In this resin composition, when a phenolic stabilizer and a sulfuric stabilizer and / or a phosphorus-based stabilizer are used in combination, the total added mass of the sulfuric stabilizer and the phosphorus-based stabilizer is preferably 0.1 times or more, more preferably 0.2 times or more, and more preferably 5 times or less, and more preferably 3 times or less, relative to the added mass of the phenolic stabilizer. If the content of the sulfuric stabilizer and the phosphorus-based stabilizer is above the lower limit, the effect of improving heat aging resistance is superior, and if it is below the upper limit, the decomposition of the resin during melt kneading of the resin composition can be further suppressed.

[0171] In this resin composition, when a phenolic stabilizer, a sulfur-based stabilizer, and / or a phosphorus-based stabilizer are included, the total content of the stabilizers is preferably 2% by mass or less per 100% by mass of the resin composition. By limiting the total content of the stabilizers to 2% by mass or less, the decomposition of the resin during melt kneading can be further suppressed.

[0172] Examples of pigments or dyes include inorganic pigments such as iron oxide, ultramarine, titanium dioxide, and carbon black. Examples of organic pigments include phthalocyanine and anthraquinone-based blue pigments, perylene and quinacridone-based red pigments, and isoindolinone-based yellow pigments. Special pigments include fluorescent pigments, metal powder pigments, and pearl pigments. Examples of dyes include nigrosine-based, perinone-based, and anthraquinone-based dyes. Various grades of these pigments and dyes are commercially available to suit the required color, and these can be used. They can be used individually or in combination of two or more.

[0173] The ratio of polymer particle group (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, even more preferably 2% by mass or more, while it is preferably 60% by mass or less, and more preferably 50% by mass or less. If the ratio of polymer particle group (C) or the composition is above the lower limit, the impact strength of the resulting molded article will be better, and if it is below the upper limit, the decrease in the fluidity and heat deformation temperature of the resin composition can be suppressed.

[0174] 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, while 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 above the lower limit, the decrease in the fluidity and heat deformation temperature of the resin composition can be suppressed, and if it is below the upper limit, the impact strength of the resulting molded article is better.

[0175] (Method for manufacturing resin compositions) The resin composition can be produced by mixing a group of polymer particles (C) or the composition with a thermoplastic resin (E) and, if necessary, additives. Methods for mixing the materials include, but are not limited to, known blending methods. For example, mixing and kneading can be done using a tumbler, V-type blender, super mixer, Nauter mixer, Banbury mixer, kneading roll, extruder, etc. As an example of a method for producing the resin composition of the present invention, a method is used in which a group of polymer particles (C) or the present composition, pelletized thermoplastic resin (E), and additives as needed are mixed using an extruder, extruded into a strand, and cut into pellets using a rotary cutter or the like. By this method, a pelletized resin composition can be obtained.

[0176] [Molded body] A molded article according to one aspect of the present invention (hereinafter also referred to as "the molded article") includes a group of polymer particles (C). This molded article may further contain component (D). This molded article may further contain thermoplastic resin (E). The molded article is preferably made of the resin composition described above.

[0177] This molded article can be produced, for example, by molding a group of polymer particles (C), this composition, or this resin composition. Examples of molding methods include those commonly used for molding thermoplastic resin compositions, such as injection molding, extrusion molding, blow molding, and calendering.

[0178] This molded product can be widely used industrially as a material in various fields such as automotive, office automation equipment, home appliances, electrical and electronic equipment, construction, lifestyle and cosmetics, and medical supplies. More specifically, it can be used as housings for electronic equipment, various parts, coatings, automotive structural components, automotive interior components, light reflectors, building structural components, and joinery. Even more specifically, it can be used as interior and exterior components for personal computer housings, mobile phone housings, portable information terminal housings, portable game console housings, printers, copiers, etc., conductive coatings, automotive interior and exterior components, building exterior materials, resin window frame components, flooring materials, and piping components.

[0179] Other embodiments of the present invention are shown below. [1] A polyorganosiloxane-containing polymer comprising a polymer (A) containing a polyorganosiloxane (A1) and a first vinyl polymer (A2), and a second vinyl polymer (B), A polyorganosiloxane-containing polymer is obtained by dispersing the polyorganosiloxane-containing polymer in a liquid epoxy resin, curing it to form a resin piece, and observing its cross-section with a transmission electron microscope. The polymer (A) has a sea-island structure in which the polyorganosiloxane (A1) is the sea component and the first vinyl polymer (A2) is the island component, and when L is the diameter of the particles of the polyorganosiloxane-containing polymer and M is the maximum domain length of the polyorganosiloxane (A1) contained in the particles, the ratio of the number of particles satisfying the following formula (1) to the total number of particles is less than 60%. M / L>0.1 ···(1) [2] The polyorganosiloxane-containing polymer according to [1], wherein the ratio of the polyorganosiloxane (A1) to 100% by mass of the polyorganosiloxane-containing polymer is 1% by mass or more and 50% by mass or less. [3] The polyorganosiloxane-containing polymer according to [1] or [2], wherein the ratio of the polyorganosiloxane (A1) to 100% by mass of the polyorganosiloxane-containing polymer is 1% by mass or more and 10% by mass or less. [4] A polyorganosiloxane-containing polymer according to any of [1] to [3] above, having a number-average particle diameter of 10 nm or more and 150 nm or less. [5] A polyorganosiloxane-containing polymer according to any of [1] to [4] above, wherein a portion of the polyorganosiloxane-containing polymer is insoluble in tetrahydrofuran, and the ratio of the polyorganosiloxane-containing polymer that is insoluble in tetrahydrofuran to 100% by mass of the polyorganosiloxane-containing polymer is 80% by mass or more and less than 100% by mass. [6] A polyorganosiloxane-containing polymer according to any of [1] to [5], wherein a portion of the polyorganosiloxane-containing polymer is soluble in tetrahydrofuran, and the weight-average molecular weight of the tetrahydrofuran-soluble polyorganosiloxane-containing polymer is 20,000 or more and 500,000 or less. [7] A polyorganosiloxane-containing polymer according to any of [1] to [6] above, wherein in the sea-island structure, the domains of the polyorganosiloxane (A1) contain a plurality of domains of the first vinyl polymer (A2). 〔8〕When the polyorganosiloxane-containing polymer is dispersed in a liquid epoxy resin and cured to form a resin piece, and the cross-section is observed with a transmission electron microscope, the polyorganosiloxane-containing polymer has a sea-island structure in which the polyorganosiloxane (A1) is the sea component, the first vinyl polymer (A2) is the first island component, and the second vinyl polymer (B) is the second island component, and is the polyorganosiloxane-containing polymer according to any one of the above [1] to [7]. 〔9〕The polyorganosiloxane-containing polymer according to any one of the above [1] to [8], wherein the ratio of the polymer (A) is 60% by mass or more and 95% by mass or less based on 100% by mass of the polyorganosiloxane-containing polymer. 〔10〕The polyorganosiloxane-containing polymer according to any one of the above [1] to [9], wherein the vinyl monomer component (a2) constituting the first vinyl polymer (A2) contains a (meth)acrylate monomer. 〔11〕The vinyl monomer component (b) constituting the second vinyl polymer (B) contains at least one selected from the group consisting of a (meth)acrylate monomer and an aromatic vinyl monomer, and the polyorganosiloxane-containing polymer according to any one of the above [1] to

[10] , wherein the total ratio of the (meth)acrylate monomer and the aromatic vinyl monomer is 50% by mass or more based on 100% by mass of the vinyl monomer component (b). 〔12〕The vinyl monomer component (b) constituting the second vinyl polymer (B) contains methyl methacrylate, and the polyorganosiloxane-containing polymer according to any one of the above [1] to

[11] , wherein the ratio of the methyl methacrylate is 50% by mass or more based on 100% by mass of the vinyl monomer component (b). 〔13〕The polyorganosiloxane-containing polymer according to any one of the above [1] to

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

[14] A composition comprising a polyorganosiloxane-containing polymer from any of [1] to

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

[15] The composition according to

[14] , 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 acid and alkali metal salts of alkylaryl phosphoric acid.

[16] The composition according to

[14] or

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

[17] Any of the compositions described in

[14] to

[16] above, 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 of the polyorganosiloxane-containing polymer and at least one component selected from the group consisting of the phosphoric acid compound and its alkali metal salt.

[18] A resin composition comprising a polyorganosiloxane-containing polymer according to any of [1] to

[13] above and a thermoplastic resin.

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

[14] to

[17] above and a thermoplastic resin.

[20] The resin composition according to

[18] or

[19] , 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.

[21] A molded article comprising any of the polyorganosiloxane-containing polymers described in [1] to

[13] above. [Examples]

[0180] The present invention will be described in more detail below with reference to manufacturing examples and embodiments. Manufacturing Examples 1-1 to 1-2 and 2-1 to 2-20 are examples of manufacturing polyorganosiloxane (A1), polymer (A), polymer particle group (C), and composition. Note that "parts" means "parts by mass," "%" means "mass percent," and "ppm" means "mass ppm." Various measurement methods are also described below.

[0181] [Measurement of solid content] A polyorganosiloxane latex with mass w1 is dried in a hot air dryer at 180°C for 30 minutes. The mass w2 of the residue after drying is measured, and the solid content [%] is calculated using the following formula (O). Solid content [%] = w² / w1 × 100 ... (O)

[0182] [Measurement of particle size] "Polyorganosiloxane (A1) latex" or "polymer particle group (C) latex" was diluted with deionized water to a solid content concentration of approximately 3% as a sample. The number-average particle diameter Dn and mass-average particle diameter Dw were measured using the aforementioned CHDF2000 particle size analyzer manufactured by MATEC, Inc. in the United States, under the following conditions. Cartridge: Dedicated capillary cartridge for particle separation (product name: C-202) Carrier fluid: Dedicated carrier fluid (product name; 2XGR500) pH of the carrier solution: Neutral, Carrier fluid flow rate: 1.4 mL / min Carrier fluid pressure: 4,000 psi (2,600 kPa) Measurement temperature: 35℃, Sample volume used: 0.1 mL.

[0183] [Powder recovery method] The polymer particle group (C) was recovered in powder form by either the coagulation method (indicated as G in Tables 1 and 2) or the spray recovery method (indicated as S in the same tables) as described below. Coagulation method: 630 parts of an aqueous solution with a calcium acetate concentration of 0.8% were heated to 50°C, and polymer particle group (C) latex was gradually added dropwise to the aqueous solution while stirring, causing coagulation. The resulting polymer particle group (C) was filtered, washed, dehydrated, and then dried to obtain polymer particle group (C) powder. Spray recovery method: Polymer particle group (C) latex was spray-dried using an atomizer-type spray dryer (Okawara Chemical Machinery Co., Ltd., L8 spray dryer) under the following processing conditions to obtain polymer particle group (C) powder. <Spray drying treatment conditions> Spraying method: Rotating disc type Disk rotation speed: 25,000 rpm Hot air temperature Inlet temperature: 130℃, outlet temperature: 60℃

[0184] [Measurement of THF-insoluble content] For polymer particle group (C), the THF-insoluble content was measured according to the following method. (1-1) 0.5 g of the sample was added to 50 mL (44.5 g) of THF to prepare a mixed solution. After standing at 25°C for 8 hours, the mixture was stirred with a stirrer for 30 minutes to dissolve the THF-soluble components. (1-2) The mixed solution is placed in a centrifuge tube whose mass has been measured, and the THF-insoluble portion and the THF-soluble portion are separated by centrifugation using a centrifuge (16000 rpm, 4 hours). (1-3) After separating the supernatant liquid containing THF-soluble components, fresh THF is added and stirred, and then centrifuged again in the same manner as in (1-2) above to wash away THF-insoluble components. (1-4) After repeating (1-3) twice, remove the supernatant. Immerse the centrifuge tube containing the remaining THF-insoluble matter in a hot water bath (80°C, 8 hours) to volatilize the THF, then vacuum dry at 65°C for 6 hours to obtain a dried sample (THF-insoluble matter adhering to the centrifuge tube). (1-5) Measure the mass of the obtained dried sample (THF insoluble matter + centrifuge tube), and calculate the THF insoluble matter content w using the following formula (k). ais Calculate the percentage (%). w ais =(w c1 -w as ) / wt×100 ···(ka) wt: Mass of the polyorganosiloxane-containing polymer particle group (C) used for measurement. w as : Mass of the centrifuge tube w c1 : Mass of THF-insoluble matter (mass including centrifuge tube)

[0185] [Measurement of weight-average molecular weight of THF-soluble components] The weight-average molecular weight of the THF-soluble components was measured by performing the following procedures (2-1) to (2-3). (2-1) From the liquid containing the THF-soluble component collected in the previous item [Measurement of THF-insoluble component], distill off THF under reduced pressure using a rotary evaporator to obtain the THF-soluble component. (2-2) Redissolve the THF-soluble component obtained in (2-1) in THF again so that the sample concentration is 0.1 to 0.3% to obtain a THF solution of the THF-soluble component. (2-3) Perform gel permeation chromatography (GPC) measurement on the THF solution of the THF-soluble component obtained in (2-2), and determine the weight average molecular weight (Mw) from the calibration curve using standard polystyrene. The measurement conditions for GPC are as follows. Apparatus: "HLC8220" manufactured by Tosoh Corporation, Column: "TSKgel SuperMultipore HZ-H" manufactured by Tosoh Corporation (inner diameter 4.6 mm × length 15 cm × 2 columns, exclusion limit 4 × 10 7 (Estimated)), Eluent: THF, Eluent flow rate: 0.35 mL / min, Measurement temperature: 40 °C, Sample injection volume: 10 μL.

[0186] [Acquisition and Image Analysis of TEM Images] Put the polymer particle group (C) into a polyethylene capsule, pour in a liquid epoxy resin (Epifome (registered trademark) R-2100, H-105, manufactured by Somal Co., Ltd.), and stir. Leave it at 25 °C for 12 hours to cure the above epoxy resin. Face out and trim the obtained resin piece using an ultramicrotome Leica EM UC7 (manufactured by Leica Microsystems Co., Ltd.). Stain the obtained resin piece with an osmium tetroxide aqueous solution (23 °C, 12 hours), and then stain it with a ruthenium tetroxide aqueous solution (23 °C, 5 hours). Cut out sections from the stained resin piece under the conditions of a cutting temperature of 23 °C, a cutting speed of 0.4 mm / second, and a thin section thickness of 50 nm, and collect them on a copper grid with a support film.

[0187] Randomly selected 0.5 μm on the surface of the collected section 2The above range was observed using a TEM (Hitachi H-7600) under conditions of an acceleration voltage of 80kV and a magnification of 200,000x, and TEM images were acquired. In the obtained TEM images, the region of the epoxy resin cured product (resin region) and the region of particles dispersed within this region were observed. Furthermore, in the particle region, the polyornosiloxane (A1) portion was identified as bright contrast, and the vinyl polymer portion as dark contrast.

[0188] From the particle regions observed in a single TEM observation image, particle regions that fall under (i) to (iii) below were excluded. (i) Particle regions that are cut off at the edge of the image. (ii) Particles whose size is less than 80% of the average particle diameter. (iii) A particle region in which there are adjacent particle regions in three or more directions, and the boundaries of each particle region are unclear.

[0189] For more than 80% of the remaining particle regions, and for more than 50 particle regions, contrast line profile measurements were performed using the following procedure to calculate the Z-values, and the average value of these values ​​was determined. The ratio of selected particle regions at this time refers to the ratio of the number of selected particle regions to the total number of particle regions observed in the image.

[0190] From the obtained TEM images, the particle region diameter L and the maximum domain length M of the polyorganosiloxane (A1) were calculated using image analysis software (ImageJ). As described above, the diameter L of a particle region was determined by creating a line profile that passes through the midpoint connecting the major and minor axes of a single particle region and cuts across the particle diameter. As described above, the maximum domain length M was determined from the region with the longest continuous length among the areas where the contrast value (Gray Value) within a single particle region obtained by line profiling continuously shows values ​​of 75% or more of the maximum value. From the obtained diameter L and maximum domain length M, the number of particle regions satisfying equation (1) below was defined as Z1, and the number of particle regions not satisfying the equation was defined as Z2. The Z value [%] was then calculated from equation (2) below. M / L>0.1 ···(1) Z-value [%] = {Z1 / (Z1+Z2)} × 100 ... (2)

[0191] <Manufacturing Example 1-1> (Manufacturing of polyorganosiloxane (A1-1)) 98 parts of a cyclic organosiloxane mixture (manufactured by Shin-Etsu Silicone Co., Ltd., product name: DMC, a mixture of cyclic organosiloxanes with 3 to 6 member rings) and 2 parts of 3-methacryloxypropylmethyldimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd., product name: KBM-502) were mixed to obtain 100 parts of an organosiloxane mixture. An aqueous solution prepared by dissolving 0.7 parts of sodium dodecylbenzenesulfonate (DBSNa, manufactured by Kao Corporation, product name: Neoperex G-15, on a solid content basis) in 300 parts of deionized water was added to the above mixture, stirred at 10,000 rpm for 5 minutes in a homomixer, and then passed through a homogenizer twice at a pressure of 20 MPa to obtain a stable premixed emulsion. Next, an aqueous solution prepared by dissolving 15 parts of dodecylbenzenesulfonic acid (DBSH, manufactured by Kao Corporation, product name: Neoperex GS) in 90 parts of deionized water was placed in a 5-liter separable flask equipped with a cooling condenser. This aqueous solution was then heated to 80°C, and the emulsion was continuously added for 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, thereby obtaining polyorganosiloxane latex (A1-1). The solid content of the polyorganosiloxane latex (A1-1) was 20%. Furthermore, the number-average particle size (Dn) of this latex, as measured by a capillary particle size analyzer, was 26 nm, and the mass-average particle size (Dw) was 35 nm, resulting in a Dw / Dn ratio of 1.35.

[0192] <Manufacturing Example 1-2> (Manufacturing of polyorganosiloxane (A1-2)) 98 parts of a cyclic organosiloxane mixture (manufactured by Shin-Etsu Silicone Co., Ltd., product name: DMC, a mixture of cyclic organosiloxanes with 3 to 6 member rings) and 2 parts of 3-methacryloxypropylmethyldimethoxysilane (KBM-502) were mixed to obtain 100 parts of an organosiloxane mixture. An aqueous solution prepared by dissolving 0.7 parts of sodium dodecylbenzenesulfonate (DBSNa) in 350 parts of deionized water was added to the mixture, stirred at 10,000 rpm for 5 minutes in a homomixer, and then passed through a homogenizer twice at a pressure of 20 MPa to obtain a stable premixed emulsion.

[0193] Next, an aqueous solution prepared by dissolving 4 parts of dodecylbenzenesulfonic acid (DBSH) in 40 parts of deionized water was placed in a 5-liter separable flask equipped with a cooling condenser. The aqueous solution was then heated to 80°C, and the emulsion was continuously added for 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, thereby obtaining polyorganosiloxane latex (A1-2).

[0194] The solid content of the polyorganosiloxane latex (A1-2) was 18% by mass. Furthermore, the number-average particle size (Dn) of this latex, as measured by a capillary particle size analyzer, was 67 nm, and the mass-average particle size (Dw) was 83 nm, resulting in a Dw / Dn ratio of 1.24.

[0195] <Manufacturing Example 2-1> (Production of polymer particle group (C-1)) Eighteen parts (3.0 parts in polymer equivalent) of the polyorganosiloxane latex (A1-1) obtained in Production Example 1-1 were taken 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 this separable flask, the atmosphere inside the flask was replaced with nitrogen by passing a nitrogen stream through it, the liquid temperature was raised to 43°C, and the mixture was stirred for 1 hour. 0.15 parts of potassium persulfate (KPS) were added to initiate radical polymerization, and the mixture was stirred for 10 hours. After confirming the exothermic polymerization peak, the mixture was cooled to 25°C and held for 15 hours to complete the polymerization, yielding a composite rubber latex.

[0196] 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 complete, the temperature was maintained at 80°C for 1 hour, then cooled to 25°C to obtain the latex of polymer particle group (C-1). The solids content of this latex was 35%, and the polymerization rate was over 99.9%. This polymerization rate represents the polymerization rate of the monomer components used throughout the entire process, from the manufacturing of the composite rubber to graft polymerization. The number-average particle size (Dn) of this latex, measured by a capillary particle size analyzer, was 94 nm, the mass-average particle size (Dw) was 105 nm, and the Dw / Dn ratio was 1.12.

[0197] Next, a powder of polymer particle group (C-1) was obtained by the coagulation method described above. The proportion of THF-insoluble matter in polymer particle group (C-1) was 95%. The weight-average molecular weight of the THF-soluble matter was 230,000.

[0198] As shown in Figure 2, the polymer particle group (C-1) had a sea-island structure with polyorganosiloxane (A1) as the sea component and vinyl polymer (A2) as the island component. The Z-value was 8%.

[0199] <Manufacturing Example 2-2> (Production of polymer particle group (C-2)) Polymer particle group (C-2) was obtained by recovering the latex of polymer particle group (C-1) obtained in Production Example 2-1 as a powder using the spray drying method described above. Since the latex after polymerization is the same, the particle size, the ratio of THF-insoluble matter, the weight-average molecular weight of the THF-soluble matter, and the Z value are the same as those of polymer particle group (C-1).

[0200] <Manufacturing Examples 2-3 to 2-6> (Manufacturing of polymer particle groups (C-3) to (C-6)) Polymer particle groups (C-3) to (C-6) were obtained in the same manner as in Production Example 2-1, except that the amount of monomer used and the powder recovery method were changed as shown in Table 1. The solidification temperature when obtaining polymer powder by coagulation was appropriately changed between 50 and 85°C according to the properties of the obtained powder.

[0201] <Manufacturing Example 2-7> (Production of polymer particle group (C-7)) Eighteen parts (3.0 parts in polymer equivalent) of the polyorganosiloxane latex (A1-1) obtained in Production Example 1-1 were taken 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 this separable flask, the atmosphere inside the flask was replaced with nitrogen by passing a nitrogen stream through it, the liquid temperature was raised to 43°C, and the mixture was stirred for 1 hour. 0.15 parts of potassium persulfate (KPS) were added to initiate radical polymerization, and the mixture was stirred for 10 hours. After confirming the exothermic polymerization peak, the mixture was cooled to 25°C and held for 15 hours to complete the polymerization, yielding a composite rubber latex.

[0202] The composite rubber latex was heated to 80°C, and 7.5 parts of methyl methacrylate (MMA) were added dropwise at a rate of 0.6 parts / minute to initiate the graft polymerization reaction. After the addition was complete, the temperature was maintained at 80°C for 1 hour. Next, 0.04 parts of potassium persulfate (KPS) were added and the mixture was stirred for 15 minutes. Then, 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 at a rate of 0.3 parts / minute to initiate the graft polymerization reaction again. After the addition was complete, the temperature was maintained at 80°C for 2 hours, 0.04 parts of potassium persulfate (KPS) were added and the mixture was stirred for another 2 hours. Finally, the mixture was cooled to 25°C to obtain the polymer particle group (C-7) latex. The solids content of this latex was 35%, and the polymerization rate was over 99.9%. This polymerization rate represents the polymerization rate of the monomer components used throughout the entire process, from the manufacture of the composite rubber to graft polymerization. The number-average particle size (Dn) of this latex, measured by a capillary particle size analyzer, was 90 nm, the mass-average particle size (Dw) was 112 nm, and the Dw / Dn ratio was 1.25.

[0203] Next, a powder of polymer particle group (C-7) was obtained by the coagulation method described above. The proportion of THF-insoluble matter in polymer particle group (C-7) was 95% by mass. The weight-average molecular weight of the THF-soluble matter was 400,000.

[0204] As shown in Figure 6, the polymer particle group (C-7) had a sea-island structure with polyorganosiloxane (A1) as the sea component and vinyl polymer (A2) as the island component. The Z-value was 8%.

[0205] <Manufacturing Example 2-8> (Manufacturing of polymer particle group (C-8)) Except for changing the amount of monomer used as shown in Table 1, the polymer particle group (C-8) powder was obtained in the same manner as in Production Example 2-7.

[0206] <Manufacturing Examples 2-9, 2-10> (Manufacture of compositions (C-9) and (C-10)) To the latex of the polymer particle group (C-1) obtained in Production Example 2-1, the amount of sodium tridecyloxyethylene phosphate (RS-610Na, manufactured by Toho Chemical Industry Co., Ltd., product name: Phosphanol® RS-610Na, based on solid content, polyoxyethylene alkyl phosphate with a tridecyl alkyl group, number of oxyethylene units in the polyoxyethylene group: 6) listed in Table 1 was added as component (D) to obtain the latex of composition (C-9) and the latex of composition (C-10).

[0207] Next, each latex was powdered by the coagulation method described above to obtain the powder of composition (C-9) and the powder of composition (C-10). In compositions (C-9) and (C-10), the proportion of THF-insoluble matter in the polymer particle group (C-1) was 95%, the weight-average molecular weight of the THF-soluble matter was 230,000, and the Z-value was 8%. The phosphorus atom content relative to the total mass of the polymer particle group (C-1) and the additional emulsifier was 230 ppm for composition (C-9) and 490 ppm for composition (C-10). The phosphorus atom content of polymer (C-1) obtained in Production Example 2-1 was less than 16 ppm.

[0208] <Manufacturing Examples 2-11, 2-12> (Manufacturing of polymer particle groups (C-11) and (C-12)) Except for changing the types and amounts of polyorganosiloxane latex, monomers, and emulsifiers used as shown in Table 2, polymer particle powders (C-11) and (C-12) were obtained in the same manner as in Production Example 2-1. The coagulation temperature for obtaining each powder was appropriately changed between 55 and 95°C according to the properties of the resulting powder.

[0209] <Manufacturing Examples 2-13 to 2-15> (Manufacturing of polymer particle groups (C-13) to (C-15)) Except for changing the types and amounts of polyorganosiloxane latex, monomers, and emulsifiers used as shown in Table 2, polymer particle groups (C-13) to (C-15) powders were obtained in the same manner as in Production Example 2-7. The coagulation temperature for obtaining each powder was appropriately changed between 55 and 75°C according to the properties of the resulting powder.

[0210] <Manufacturing Example 2-16> (Manufacturing of polymer particle group (C-16)) 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 in a 5-liter separable flask, and the atmosphere inside the flask was replaced with nitrogen by stirring for 1 hour while passing a nitrogen stream through the mixture. After raising the liquid temperature to 80°C, 0.05 parts of potassium persulfate (KPS) were added and the mixture was stirred for 180 minutes. Then, it was cooled to 25°C and allowed to stand for 18 hours. 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, and the mixture was stirred at 25°C for 90 minutes while passing a nitrogen stream through it. After that, the liquid temperature was raised to 43°C and stirred for 1 hour. 0.15 parts of potassium persulfate (KPS) were added to initiate radical polymerization, and the mixture was stirred for 10 hours. After confirming the exothermic polymerization peak, the mixture was cooled to 25°C and held for 15 hours to complete the polymerization, yielding a composite rubber latex.

[0211] The composite rubber latex was heated to 80°C, and 20 parts of methyl methacrylate (MMA) were added dropwise at a rate of 0.6 parts / minute to initiate the graft polymerization reaction. After the addition was complete, the temperature was maintained at 80°C for 1 hour, then cooled to 25°C to obtain latex containing polymer particles (C-16). The solids content of this latex was 35%, and the polymerization rate was over 99.9%. This polymerization rate represents the polymerization rate of the monomer components used throughout the entire process, from acrylic rubber manufacturing to graft polymerization. The number-average particle size (Dn) of this latex, measured by a capillary particle size analyzer, was 88 nm, the mass-average particle size (Dw) was 94 nm, and the Dw / Dn ratio was 1.07.

[0212] Next, the polymer particles (C-16) were powdered using the coagulation method described above. The proportion of THF-insoluble matter in polymer particles (C-16) was 96%. The weight-average molecular weight of the THF-soluble matter was 170,000. Since polymer particles (C-16) do not contain polyorganosiloxane (A1) and consist only of vinyl polymer (A2), TEM observation was not performed.

[0213] <Manufacturing Example 2-17> (Manufacturing of polymer particle group (C-17)) The polymer particle group (C-17) latex was obtained in the same manner as in Production Example 2-1, except that the amount of monomer used was changed as shown in Table 2. The solid content of this latex was 35%, and the polymerization rate was over 99.9%. Furthermore, the number-average particle size (Dn) measured by a capillary particle size analyzer was 98 nm, the mass-average particle size (Dw) was 108 nm, and the Dw / Dn ratio was 1.11.

[0214] Next, the polymer particles (C-17) were powdered using the coagulation method described above. The proportion of THF-insoluble matter in the polymer particles (C-17) was 79%. The weight-average molecular weight of the THF-soluble matter was 410,000. The Z-value was 68%.

[0215] <Manufacturing Example 2-18> (Manufacturing of polymer particle group (C-18)) Eighteen parts (3.0 parts in polymer equivalent) of the polyorganosiloxane latex (A1-1) obtained in Production Example 1-1 were taken 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 this separable flask, the atmosphere inside the flask was replaced with nitrogen by passing a nitrogen stream through it, the liquid temperature was raised to 65°C, and the mixture was stirred for 1 hour.

[0216] 0.25 parts of potassium persulfate (KPS) were added to initiate radical polymerization. Subsequently, the liquid temperature was raised to 80°C and maintained for 1 hour to complete the polymerization, yielding a composite rubber latex.

[0217] While maintaining the liquid temperature of the latex 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 temperature was maintained at 80°C for 1 hour, then cooled to 25°C to obtain latex containing polymer particles (C-18).

[0218] The latex had a solid content of 30% by mass, and its polymerization rate was 99.9% or higher. Furthermore, the number-average particle size (Dn) measured by a capillary particle size analyzer was 98 nm, the mass-average particle size (Dw) was 113 nm, and the Dw / Dn ratio was 1.16.

[0219] Next, 630 parts of an aqueous solution containing 0.8% by mass of calcium acetate were heated to 70°C, and the obtained graft copolymer latex was gradually added dropwise to this aqueous solution while stirring, allowing it to solidify. The obtained graft copolymer was filtered, washed, dehydrated, and then dried to obtain a powder of polymer particles (C-18). The THF-insoluble fraction of polymer particles (C-18) was 93% by mass. The weight-average molecular weight of the THF-soluble fraction was 190,000. The Z-value was 66%.

[0220] <Manufacturing Example 2-19> (Manufacturing of polymer particle group (C-19)) Eighteen parts (3.0 parts in polymer equivalent) of the polyorganosiloxane latex (A1-1) obtained in Production Example 1-1 were taken 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 t-butyl hydroperoxide (t-BH), and 0.3 parts of sodium dodecylbenzenesulfonate (DBSNa) were added to this separable flask, the atmosphere inside the flask was replaced with nitrogen by passing a nitrogen stream through it, the liquid temperature was raised to 50°C, and the mixture was stirred for 1 hour.

[0221] 5 parts of deionized water containing 0.0005 parts of ferrous sulfate heptahydrate (Fe), 0.0015 parts of ethylenediaminetetraacetate disodium dihydrate (EDTA), and 0.2 parts of sodium formaldehyde sulfoxylate (SFS) were added all at once to initiate radical polymerization. The mixture was then held for 1 hour to complete the polymerization and obtain a composite rubber latex.

[0222] While maintaining the liquid temperature of the latex at 50°C, a mixture of 20 parts methyl methacrylate (MMA) and 0.05 parts t-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 temperature was maintained at 50°C for 1 hour, then cooled to 25°C to obtain latex containing polymer particles (C-19).

[0223] The latex had a solid content of 35% by mass, and its polymerization rate was 99.9% or higher. Furthermore, the number-average particle size (Dn) of this latex, as measured by a capillary particle size analyzer, was 96 nm, and the mass-average particle size (Dw) was 106 nm, resulting in a Dw / Dn ratio of 1.11.

[0224] Next, 630 parts of an aqueous solution containing 0.8% by mass of calcium acetate were heated to 70°C, and the obtained graft copolymer latex was gradually added dropwise to this aqueous solution while stirring, allowing it to solidify. The obtained graft copolymer was filtered, washed, dehydrated, and then dried to obtain a powder of polymer particles (C-19). The THF-insoluble fraction of polymer particles (C-19) was 93% by mass. The weight-average molecular weight of the THF-soluble fraction was 170,000. The Z-value was 96%.

[0225] <Manufacturing Example 2-20> (Manufacturing of polymer particle group (C-20)) A polymer particle group (C-20) powder was obtained in the same manner as in Production Example 2-19, except that the type and amount of monomers used were changed as shown in Table 2. The THF-insoluble fraction of polymer particle group (C-20) was 85% by mass. The weight-average molecular weight of the THF-soluble fraction was 150,000. The Z-value was 68%.

[0226] [Table 1]

[0227] [Table 2]

[0228] <Examples 1-14, Comparative Examples 1-11> The polymer obtained in the above production example, styrene-acrylonitrile copolymer, carbon black (CB, manufactured by Mitsubishi Chemical Corporation, product name: #960B), and magnesium stearate (MgST, manufactured by Nacalai Tesque Co., Ltd.) were blended in the proportions shown in Tables 3 to 6 to obtain a mixture. This mixture was supplied to a devolatile twin-screw extruder (manufactured by Toshiba Machine Co., Ltd., product name: TEM-35B) heated to a barrel temperature of 240°C and kneaded to produce pellets of each resin composition.

[0229] Here, the following styrene-acrylonitrile copolymers were used. SAN-1: Manufactured by Techno UMG Co., Ltd., Product name: SR-56B (AN content 33%). SAN-2: Manufactured by Techno UMG Co., Ltd., Product name: AP-H (AN content 27%). SAN-3: Manufactured by Techno UMG Co., Ltd., Product name: AP-A (AN content 30%). The AN content is the mass ratio of acrylonitrile units to 100% styrene-acrylonitrile copolymer.

[0230] Each pellet was injection-molded under the following conditions to produce test specimens for evaluation. Injection molding machine: Sumitomo Heavy Industries, Ltd., SE100DU (product name) Cylinder temperature: 240℃, Mold temperature: 80℃ Specification of the test specimen: Test specimen A: Length 80mm x Width 10mm x Thickness 4mm Test specimen B: Length 100mm x Width 50mm x Thickness 2mm

[0231] [Charpy impact test] A TYPE A notch, in accordance with ISO 179-1, was engraved on test specimen A, and the Charpy impact strength was measured at 23°C and -30°C. A higher value indicates better impact resistance, which is preferable.

[0232] [Color development test] As an indicator of colored appearance, the lightness (L) of test piece B is used. * The color was measured using a spectrophotometer (SE7700 (product name) manufactured by Nippon Denshoku Industries Co., Ltd.) with a C light source and a 2-degree field of view, using the reflected light measurement method. In the embodiment of this application, since the color is black, a lower numerical value indicates a better color appearance (jet blackness), which is preferable.

[0233] [Weather resistance test] A weather resistance test was conducted using the same molded material (flat plate) as in the color development test described above, under the following irradiation conditions. "Irradiation conditions" Test equipment: Daipla Metal Weather, manufactured by Daipla Wintes Co., Ltd., model KW-R5TP-A,5 Tank temperature: 50℃ setting, UV irradiation conditions: 65mW / cm 2 setting, (Measured using UIT-101 / UVD-365PD illuminance meter manufactured by Ushio Inc., measurement wavelength 330-390nm, peak sensitivity wavelength 365nm) Filter: KF-1 filter (transmission wavelength range: 295nm~780nm) Test environment: 20 hours of irradiation only, followed by 4 hours of darkness (24 hours / 1 cycle). Test duration: 96 hours (4 cycles).

[0234] Yellowness (YI, compliant with JIS K7105) and brightness (L) before and after weather resistance testing. * ) and chromaticity (a * , b * The color temperature (based on JIS Z8781-4) was measured using a spectrophotometer (SE7700 (product name) manufactured by Nippon Denshoku Industries Co., Ltd.) with a C light source and a 2-degree field of view, using the reflected light measurement method.

[0235] The degree of yellowness before the weathering test (YI1) was defined as the initial degree of yellowness (YI). The change in yellowness (ΔYI) was calculated from the yellowness before the weathering test (YI1) and the yellowness after the weathering test (YI2) using the following formula (c). Also, the color difference (ΔE * ab ) the brightness (L) before the weather resistance test.* 1) and chromaticity (a * 1, b * 1) and the brightness (L) after the weather resistance test. * 2) and chromaticity (a * 2, b * 2) was calculated using the following formula (ii). Equation (c): ΔYI = YI2 - YI1 Equation (ii): ΔE* ab =((L * 2-L * 1) + (a * 2-a * 1) + (b * 2-b * 1)) 0.5 A lower initial yellowness indicates better heat resistance and color change during molding, which is preferable. Furthermore, smaller changes in yellowness and color differences indicate better weather resistance, which is also preferable.

[0236] [Table 3]

[0237] Examples 1-6 exhibited excellent impact strength and colored appearance. In Comparative Example 1, the impact strength was extremely low because it did not contain polymer particle group (C). In Comparative Example 2, an acrylic polymer that did not contain polyorganosiloxane was used, resulting in a lower impact strength. In Comparative Examples 3-5, polymer particle group (C) with a Z value of 60% or higher was used, resulting in lower impact strength and colored appearance.

[0238] [Table 4]

[0239] Examples 7-12 exhibited excellent impact strength and colored appearance. In Comparative Example 6, a group of polymer particles (C) with a Z value of 60% or higher was used, resulting in lower impact strength and colored appearance.

[0240] [Table 5]

[0241] Example 13 exhibited excellent impact strength and colored appearance. In Comparative Examples 8 and 9, the polymer particle group (C) with a Z value of 60% or higher was used, resulting in lower impact strength and colored appearance.

[0242] [Table 6]

[0243] Example 14 exhibited excellent impact strength and weather resistance. In Comparative Examples 10 and 11, polymer particle group (C) with a Z value of 60% or higher was used, resulting in low impact strength, colored appearance, heat discoloration resistance, and weather resistance.

[0244] <Examples 15-25, Comparative Examples 12-19> The polyorganosiloxane-containing polymers obtained in the above production example, methacrylic resin (PMMA), and various organic dyes were blended in the proportions shown in Tables 7 and 8 to obtain mixtures. These mixtures were supplied to a devolatile twin-screw extruder (Toshiba Machine Co., Ltd., TEM-35B (product name)) heated to a barrel temperature of 250°C and kneaded to produce pellets of each resin composition.

[0245] Here, as the methacrylic resin (PMMA), we used Acrypet VH001 (trade name, containing 90% or more methyl methacrylate units, manufactured by Mitsubishi Chemical Corporation). In addition, the following were used as coloring agents. (OD-1): Organic dye, manufactured by Mitsubishi Chemical Corporation, Diarezin Green C. (OD-2): Organic dye, manufactured by Mitsubishi Chemical Corporation, Diarezin Red A. (OD-3): Organic dye, manufactured by Mitsubishi Chemical Corporation, Diarezin Blue G. CB: Carbon Black, manufactured by Mitsubishi Chemical Corporation, #960B.

[0246] Test specimens for evaluation were prepared by injection molding resin composition pellets under the following conditions. Injection molding machine: Toshiba Machine Co., Ltd. injection molding machine, model number EC20PNII (product name) Cylinder temperature: 250℃, Mold temperature: 60℃ Specification of the test specimen: Test specimen A: Length 80mm x Width 10mm x Thickness 4mm Test specimen C: Length 50mm x Width 50mm x Thickness 3mm

[0247] [Charpy impact strength] A TYPE A notch, in accordance with ISO 179-1, was engraved on test specimen A, and the Charpy impact strength was measured at 23°C and -30°C. A higher value indicates better impact resistance, which is preferable.

[0248] [Color development test] As an indicator of the colored appearance of the resin composition, the lightness (L) is determined according to the following method. * The following was evaluated: Using a spectrocolorimeter (product name: SD7000, manufactured by Nippon Denshoku Industries Co., Ltd.), the hue of the above test piece C was measured using the SCE method, and L was determined in accordance with ISO 11664-4. * The following was sought. In the embodiment of this application, since the material is colored black, a lower value indicates a better colored appearance (jet blackness), which is preferable.

[0249] [Table 7]

[0250] Examples 15-18 exhibited excellent impact strength and colored appearance. Comparative Example 12 did not contain polymer particle group (C), and therefore exhibited extremely low impact strength. In Comparative Examples 13-15, a polymer particle group (C) with a Z value of 60% or higher was used, resulting in a poor balance between impact strength and colored appearance.

[0251] [Table 8]

[0252] Examples 19-25 exhibited excellent impact strength and colored appearance. Comparative Example 16 exhibited extremely low impact strength because it did not contain polymer particle group (C). In Comparative Examples 17-19, polymer particle group (C) with a Z value of 60% or higher was used, resulting in lower impact strength and colored appearance.

[0253] <Examples 26-31, Comparative Examples 20-34> The polyorganosiloxane-containing polymers obtained in the above production example, various additives, and various thermoplastic resins were blended in the ratios shown in Tables 9 to 12 to obtain mixtures. These mixtures were fed into a devolatile twin-screw extruder (Ikegai Co., Ltd., PCM-30 (product name)) and kneaded to produce pellets of each resin composition.

[0254] The following thermoplastic resins were used here. PC: Polycarbonate resin (Yupilon S-2000F, manufactured by Mitsubishi Engineering Plastics Corporation, viscosity-average molecular weight 24,000). SAN-2: Styrene-acrylonitrile copolymer (AP-H, manufactured by Techno UMG Co., Ltd.). PET: Polyethylene terephthalate resin (TRN8550FF, manufactured by Teijin Limited). PCGF-1: Glass fiber-reinforced polycarbonate resin (Yupilon GS2020MR2, manufactured by Mitsubishi Engineering Plastics Corporation, with 20% glass fiber by mass added).

[0255] Test specimens for evaluation were prepared by injection molding pellets of the resin composition. Injection molding machine: Sumitomo Heavy Industries, Ltd., SE100DU (product name) Specification of the test specimen: Test specimen A: Length 80mm x Width 10mm x Thickness 4mm Test specimen D: Length 127mm x Width 12.7mm x Thickness 1.6mm At this time, the extrusion conditions and injection molding conditions were appropriately changed as follows, taking into consideration the fluidity of the molding resin. (Example 26, Comparative Examples 20-22) Extrusion barrel temperature: 280°C, injection cylinder temperature: 280°C, mold temperature: 80°C. (Examples 27-28, Comparative Examples 23-26) Extrusion barrel temperature: 260°C, injection cylinder temperature: 260°C, mold temperature: 80°C. (Examples 29-30, Comparative Examples 27-30) Extrusion barrel temperature: 280°C, injection cylinder temperature: 300°C, mold temperature: 70°C. (Example 31, Comparative Examples 31-34) Extrusion barrel temperature: 300°C, injection cylinder temperature: 300°C, mold temperature: 90°C.

[0256] [Charpy impact strength] A TYPE A notch, in accordance with ISO 179-1, was engraved on test specimen A, and its Charpy impact strength was measured. A higher value indicates better impact resistance, which is preferable. In this embodiment, in some impact tests, the impact resistance was high and the test specimen did not completely break. In this case, since the accurate impact value could not be calculated, it was indicated as NB in ​​the table.

[0257] [Table 9]

[0258] Example 26 exhibited excellent impact strength. Comparative Example 20 did not contain polymer particle group (C), and therefore exhibited extremely low impact strength. In comparative examples 21 and 22, the impact strength was low because polymer particle group (C) with a Z value of 60% or higher was used.

[0259] [Table 10]

[0260] Examples 27-28 exhibited excellent impact strength. Comparative Example 23 did not contain polymer particle group (C), and therefore exhibited extremely low impact strength. In comparative examples 24-26, the impact strength was low because polymer particle group (C) with a Z value of 60% or higher was used.

[0261] [Table 11]

[0262] Examples 29-30 exhibited excellent impact strength. Comparative Example 27 did not contain polymer particle group (C), and therefore exhibited extremely low impact strength. In comparative examples 28-30, the impact strength was low because polymer particle group (C) with a Z value of 60% or higher was used.

[0263] [Table 12]

[0264] Example 31 exhibited excellent impact strength. Comparative Example 31 did not contain polymer particle group (C), and therefore its impact strength was extremely low. In comparative examples 32-34, the impact strength was low because polymer particle group (C) with a Z value of 60% or higher was used.

[0265] <Examples 32-33, Comparative Examples 35-36> The polyorganosiloxane-containing polymers obtained in the above production example, various additives, and polyacetal resin (POM) were blended in the proportions shown in Table 13 to obtain mixtures. These mixtures were supplied to a devolatile twin-screw extruder (manufactured by Ikegai Co., Ltd., product name PCM-30) heated to a barrel temperature of 180°C and kneaded to produce pellets of each resin composition.

[0266] Here, HOSTAFORM C9021 (product name, manufactured by Celanese Japan Co., Ltd.) was used as the polyacetal resin (POM). In addition, the following were used as various auxiliary agents. St-Ca: Calcium stearate (Calcium stearate GF-200, manufactured by NOF Corporation). Irg245: Phenolic antioxidant (Irganox 245, manufactured by Ciba Japan Co., Ltd.).

[0267] Test specimens for evaluation were prepared by injection molding resin composition pellets under the following conditions. Injection molding machine: Sumitomo Heavy Industries, Ltd., SE100DU (product name) Cylinder temperature: 205℃, Mold temperature: 70℃ Specification of the test specimen: Test specimen A: Length 80mm x Width 10mm x Thickness 4mm

[0268] [Charpy impact strength] A TYPE A notch, in accordance with ISO 179-1, was engraved on test specimen A, and the Charpy impact strength was measured at 23°C and 30°C. A higher value indicates better impact resistance, which is preferable.

[0269] [Table 13]

[0270] Examples 32-33 exhibited excellent impact strength. Comparative Example 35 did not contain polymer particle group (C), and therefore exhibited extremely low impact strength. In Comparative Example 36, the impact strength was low because a group of polymer particles (C) with a Z value of 60% or higher was used.

[0271] <Examples 34-35, Comparative Examples 37-38> The polyorganosiloxane-containing polymers and polyvinyl chloride resins obtained in the above production examples were blended in the proportions shown in Table 14 to obtain a mixture. Here, the polyvinyl chloride resin consists of 100 parts of polyvinyl chloride resin (product name: TK-1000, manufactured by Shin-Etsu Chemical Co., Ltd., average degree of polymerization 1050), 3 parts of Ca / Zn composite stabilizer (product name: HT-547A, manufactured by Nitto Chemical Industries, Ltd.), 6 parts of calcium carbonate (product name: μ-powder 3S, manufactured by Bihoku Powdering Industry Co., Ltd.), 3 parts of titanium dioxide (product name: Typeque R830, manufactured by Ishihara Sangyo Co., Ltd.), 0.5 parts of glycerin fatty acid ester (product name: Loxiol GH-4, manufactured by Emery Oleochemicals Japan Co., Ltd.), 0.2 parts of polymer composite ester (product name: Loxiol VPN963, manufactured by Emery Oleochemicals Japan Co., Ltd.), 0.3 parts of polymer composite ester (product name: Loxiol G70S, manufactured by Emery Oleochemicals Japan Co., Ltd.), and polyethylene wax (product name: Loxiol 0.2 parts of VPN233 (manufactured by Emery Oleochemicals Japan Co., Ltd.) and an acrylic processing aid (product name: Metabren P-570A, manufactured by Mitsubishi Chemical Corporation) were supplied to a Henschel mixer and uniformly mixed, and the resulting powder was used.

[0272] The mixture of the aforementioned vinyl chloride resin and each polyorganosiloxane-containing polymer was melt-kneaded for 5 minutes at 190°C and a roll spacing of 0.4 mm using an 8-inch dielectric heating test roll (manufactured by Kansai Roll Co., Ltd.) to obtain a sheet-like molded body. The obtained sheet-like molded body was heated and 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 and used for evaluation. Test specimen A: Length 80mm x Width 10mm x Thickness 4mm

[0273] [Charpy impact strength] A TYPE A notch, in accordance with ISO 179-1, was engraved on test specimen A, and the Charpy impact strength was measured at 23°C and -10°C. A higher value indicates better impact resistance, which is preferable. In this example, in some impact tests, the impact resistance was high and the test specimen did not completely break. In this case, since an accurate impact value could not be calculated, it was indicated as NB in ​​the table. In this case, it can be said that the impact strength is superior to when the specimen broke.

[0274] [Table 14]

[0275] Examples 34-35 exhibited excellent impact strength. Comparative Example 37 did not contain polymer particle group (C), and therefore its impact strength was extremely low. In Comparative Example 38, the impact strength was low because a group of polymer particles (C) with a Z value of 60% or higher was used.

[0276] <Example 36, Comparative Examples 39-40> The polyorganosiloxane-containing polymers and polyamide resins (PA) obtained in the above production examples were blended in the proportions shown in Table 15 to obtain mixtures. These mixtures were dried at 80°C for 12 hours, and then supplied to a devolatile twin-screw extruder (Ikegai Co., Ltd., PCM-30 (product name)) heated to a barrel temperature of 250°C for kneading to produce pellets of each resin composition.

[0277] Here, UBE Nylon 1022B (trade name, Polyamide 6, manufactured by Ube Industries, Ltd.) was used as the polyamide resin (PA).

[0278] Test specimens for evaluation were prepared by injection molding resin composition pellets under the following conditions. Injection molding machine: Sumitomo Heavy Industries, Ltd., SE100DU (product name) Cylinder temperature: 250℃, Mold temperature: 80℃ Specification of the test specimen: Test specimen A: Length 80mm x Width 10mm x Thickness 4mm

[0279] [Charpy impact strength] A TYPE A notch, in accordance with ISO 179-1, was engraved on test specimen A, and the Charpy impact strength was measured under completely dry conditions at 23°C and -40°C. A higher value indicates better impact resistance and is therefore preferable.

[0280] [Table 15]

[0281] Example 36 exhibited excellent impact strength. Comparative Example 39 did not contain polymer particle group (C), and therefore its impact strength was extremely low. In Comparative Example 40, the impact strength was low because a group of polymer particles (C) with a Z value of 60% or higher was used.

[0282] <Example 37, Comparative Examples 41-42> The polyorganosiloxane-containing polymers and polylactic acid resin (PLA) obtained in the above production example were blended in the proportions shown in Table 16 to obtain mixtures. These mixtures were supplied to a devolatile twin-screw extruder (manufactured by Ikegai Co., Ltd., product name PCM-30) heated to a barrel temperature of 200°C and kneaded to produce pellets of each resin composition.

[0283] Here, Ingeo Biopolymer 2003D (trade name, manufactured by NatureWorks LLC) was used as the polylactic acid resin (PLA).

[0284] Test specimens for evaluation were prepared by injection molding resin composition pellets under the following conditions. Injection molding machine: Sumitomo Heavy Industries, Ltd., SE100DU (product name) Cylinder temperature: 200℃, Mold temperature: 30℃ Specification of the test specimen: Test specimen A: Length 80mm x Width 10mm x Thickness 4mm

[0285] [Charpy impact strength] For specimen A, a TYPE A notch in accordance with ISO 179-1 was engraved, and the Charpy impact strength was measured at 23°C. Under annealing conditions, for specimen A, a TYPE A notch in accordance with ISO 179-1 was engraved, left in a 100°C oven for 3 hours, then cooled to 23°C, and the Charpy impact strength was measured. In all cases, a higher numerical value indicates better impact resistance, which is preferable.

[0286] [Table 16]

[0287] Example 37 exhibited excellent impact strength. Comparative Example 41 did not contain polymer particle group (C), and therefore its impact strength was extremely low. In Comparative Example 42, the impact strength was low because a group of polymer particles (C) with a Z value of 60% or higher was used.

[0288] <Examples 38-39, Comparative Examples 43-44> The composition and polymer particle group (C-1) obtained in Production Example 2-10 were blended with polybutylene terephthalate (PBT, Novaduran 5010R5, manufactured by Mitsubishi Engineering Plastics Corporation) and polycarbonate (PC, Yupiron S-2000F, manufactured by Mitsubishi Engineering Plastics Corporation, viscosity-average molecular weight 24,000) in the proportions shown in Table 17 to obtain a mixture. This mixture was supplied to a devolatile twin-screw extruder (manufactured by Ikegai Co., Ltd., product name PCM-30) heated to a barrel temperature of 260°C and kneaded to produce pellets of each resin composition.

[0289] Each pellet was injection-molded under the following conditions to produce test specimens for evaluation. Injection molding machine: Sumitomo Heavy Industries, Ltd., SE100DU (product name) Cylinder temperature: 260℃, Mold temperature: 60℃ Specification of the test specimen: Test specimen A: Length 80mm x Width 10mm x Thickness 4mm

[0290] [Charpy impact test] A TYPE A notch, in accordance with ISO 179-1, was engraved on test specimen A, and the Charpy impact strength was measured at 23°C and -30°C. A higher value indicates better impact resistance, which is preferable.

[0291] [Melting fluidity] Each pellet was injection molded 15 times consecutively under the following conditions, and its spiral flow length (SFL) was evaluated. Table 15 shows the maximum and minimum SFL values, and their difference ΔSFL (maximum SFL - minimum SFL) out of the 15 molds. A higher value indicates higher melt flowability, which is preferable. Furthermore, a smaller difference between the minimum and maximum values ​​indicates better molding stability, which is also preferable. Injection molding machine: Sumitomo Heavy Industries, Ltd., SE100DU (product name) Cylinder temperature: 300°C, Mold temperature: 70°C, Injection speed: 20 mm / sec, Injection pressure: 50 MPa

[0292] [Table 17]

[0293] Example 38 exhibited excellent impact strength, melt flowability, and molding stability. Example 39 exhibited excellent impact strength and melt flow properties. However, because it did not contain component (D), its molding stability was lower than that of Example 41. In Comparative Example 43, the impact strength was low because polymer particle group (C) was not used. In Comparative Example 44, a group of polymer particles (C) with a Z value of 60% or higher was used, resulting in low impact strength, melt flowability, and molding stability.

[0294] <Examples 40-42, Comparative Examples 45-46> Each of the compositions obtained in Production Examples 2-9 to 2-10, polymer particle group (C-1), polycarbonate (PC, Yupiron S-2000F, manufactured by Mitsubishi Engineering Plastics Corporation, viscosity-average molecular weight 24,000), and polyethylene terephthalate (PET, TRN8550FF, manufactured by Teijin Limited) were blended in the proportions shown in Table 18 to obtain a mixture. This mixture was supplied to a devolatile twin-screw extruder (manufactured by Ikegai Co., Ltd., product name PCM-30) heated to a barrel temperature of 280°C and kneaded to produce pellets of each resin composition.

[0295] Each pellet was injection-molded under the following conditions to produce test specimens for evaluation. Injection molding machine: Sumitomo Heavy Industries, Ltd., SE100DU (product name) Cylinder temperature: 300℃, Mold temperature: 70℃ Specification of the test specimen: Test specimen A: Length 80mm x Width 10mm x Thickness 4mm

[0296] [Charpy impact test] A TYPE A notch, in accordance with ISO 179-1, was engraved on test specimen A, and the Charpy impact strength was measured at 23°C and -30°C. A higher value indicates better impact resistance, which is preferable.

[0297] [Melting fluidity] Each pellet was injection molded 15 times consecutively under the following conditions, and its spiral flow length (SFL) was evaluated. Table 15 shows the maximum and minimum SFL values, and their difference ΔSFL (maximum SFL - minimum SFL) out of the 15 molds. A higher value indicates higher melt flowability, which is preferable. Furthermore, a smaller difference between the minimum and maximum values ​​indicates better molding stability, which is also preferable. Injection molding machine: Sumitomo Heavy Industries, Ltd., SE100DU (product name) Cylinder temperature: 300°C, Mold temperature: 70°C, Injection speed: 20 mm / sec, Injection pressure: 50 MPa

[0298] [Table 18]

[0299] Examples 40-41 exhibited excellent impact strength, melt fluidity, and molding stability. Example 42 exhibited excellent impact strength and melt flow properties. However, because it did not contain component (D), its molding stability was lower compared to Examples 40-41. In Comparative Example 45, the impact strength and fluidity were low because polymer particle group (C) was not used. In Comparative Example 46, a group of polymer particles (C) with a Z value of 60% or higher was used, resulting in low impact strength, melt flowability, and molding stability.

[0300] <Examples 43-44, Comparative Examples 47-48> The composition and polymer (C-1) obtained in Production Example 2-10 were blended with glass fiber-added polycarbonate resin (PCGF-2, Yupiron GSH2030R2, manufactured by Mitsubishi Engineering Plastics Corporation, with 30% by mass of glass fiber added) and polyethylene terephthalate (PET, TRN8550FF, manufactured by Teijin Limited) in the proportions shown in Table 19 to obtain a mixture. This mixture was supplied to a devolatile twin-screw extruder (manufactured by Ikegai Co., Ltd., product name PCM-30) heated to a barrel temperature of 300°C and kneaded to produce pellets of each resin composition.

[0301] Each pellet was injection-molded under the following conditions to produce test specimens for evaluation. Injection molding machine: Sumitomo Heavy Industries, Ltd., SE100DU (product name) Cylinder temperature: 300℃, Mold temperature: 70℃ Specification of the test specimen: Test specimen A: Length 80mm x Width 10mm x Thickness 4mm

[0302] [Charpy impact test] A TYPE A notch, in accordance with ISO 179-1, was engraved on test specimen A, and the Charpy impact strength was measured at 23°C and -30°C. A higher value indicates better impact resistance, which is preferable.

[0303] [Melting fluidity] Each pellet was injection molded 15 times consecutively under the following conditions, and its spiral flow length (SFL) was evaluated. Table 15 shows the maximum and minimum SFL values, and their difference ΔSFL (maximum SFL - minimum SFL) out of the 15 molds. A higher value indicates higher melt flowability, which is preferable. Furthermore, a smaller difference between the minimum and maximum values ​​indicates better molding stability, which is also preferable. Injection molding machine: Sumitomo Heavy Industries, Ltd., SE100DU (product name) Cylinder temperature: 300°C, Mold temperature: 70°C, Injection speed: 20 mm / sec, Injection pressure: 50 MPa

[0304] [Table 19]

[0305] Example 43 exhibited excellent impact strength, melt fluidity, and molding stability. Example 44 exhibited excellent impact strength and melt flow properties. However, because it did not contain component (D), its molding stability was lower than that of Example 43. In Comparative Example 47, the impact strength and fluidity were low because polymer particle group (C) was not used. In Comparative Example 48, a group of polymer particles (C) with a Z value of 60% or higher was used, resulting in low impact strength, melt flowability, and molding stability.

Claims

1. A group of polyorganosiloxane-containing polymer particles comprising a polymer (A) containing a polyorganosiloxane (A1) and a first vinyl polymer (A2), and a second vinyl polymer (B), A group of polyorganosiloxane-containing polymer particles in which, when a cross-section of a resin piece obtained by dispersing the group of polyorganosiloxane-containing polymer particles in a resin is observed with a transmission electron microscope, the diameter of each particle in the group of polyorganosiloxane-containing polymer particles is L, and the maximum domain length of the polyorganosiloxane (A1) is M, the proportion of particles that satisfy the following formula (1) is less than 60%. M / L>0.1...(1)

2. The polyorganosiloxane-containing polymer particle group according to claim 1, wherein the ratio of the polyorganosiloxane (A1) to 100% by mass of the polyorganosiloxane-containing polymer particle group is 1% by mass or more and 50% by mass or less.

3. The polyorganosiloxane-containing polymer particle group according to claim 1 or 2, wherein the ratio of the polyorganosiloxane (A1) to 100% by mass of the polyorganosiloxane-containing polymer particle group is 1% by mass or more and 10% by mass or less.

4. A group of polyorganosiloxane-containing polymer particles according to any one of claims 1 to 3, wherein the number-average particle diameter is 10 nm or more and 150 nm or less.

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

6. A group of polyorganosiloxane-containing polymer particles according to any one of claims 1 to 5, wherein a portion of each particle of the group of polyorganosiloxane-containing polymer particles is soluble in tetrahydrofuran, and the weight-average molecular weight of the group of polyorganosiloxane-containing polymer particles soluble in tetrahydrofuran is 20,000 or more and 500,000 or less.

7. When the cross-section of the resin piece is observed with a transmission electron microscope, the polymer (A) has a sea-island structure in which the polyorganosiloxane (A1) is the sea component and the first vinyl polymer (A2) is the island component. The polyorganosiloxane-containing polymer particle group according to any one of claims 1 to 6, wherein in the sea-island structure, a plurality of domains of the first vinyl polymer (A2) are included in the domains of the polyorganosiloxane (A1).

8. The polyorganosiloxane-containing polymer particle group according to any one of claims 1 to 7, wherein when the cross-section of the resin piece is observed with a transmission electron microscope, each particle of the polyorganosiloxane-containing polymer particle group has a sea-island structure in which the polyorganosiloxane (A1) is the sea component, the first vinyl polymer (A2) is the first island component, and the second vinyl polymer (B) is the second island component.

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

10. The polyorganosiloxane-containing polymer particle group according to any one of claims 1 to 9, wherein the vinyl monomer component (a2) constituting the first vinyl polymer (A2) includes a monofunctional (meth)acrylate monomer.

11. The vinyl monomer component (b) constituting the second vinyl polymer (B) includes at least one selected from the group consisting of (meth)acrylate monomers and aromatic vinyl monomers. The polyorganosiloxane-containing polymer particle group according to any one of claims 1 to 10, wherein the total ratio of the (meth)acrylate monomer and the aromatic vinyl monomer is 50% by mass or more with respect to 100% by mass of the vinyl monomer component (b).

12. The vinyl monomer component (b) constituting the second vinyl polymer (B) contains methyl methacrylate. The polyorganosiloxane-containing polymer particle group according to any one of claims 1 to 11, wherein the ratio of methyl methacrylate to 100% by mass of the vinyl monomer component (b) is 50% by mass or more.

13. The polyorganosiloxane-containing polymer particle group according to any one of claims 1 to 12, wherein the polymer (A) is a polymer obtained by polymerizing a vinyl monomer component (a2) constituting the first vinyl polymer (A2) in the presence of a latex containing the polyorganosiloxane (A1).

14. A composition comprising a group of polyorganosiloxane-containing polymer particles according to any one of claims 1 to 13, and at least one component selected from the group consisting of phosphoric acid compounds and alkali metal salts thereof.

15. The composition according to claim 14, 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 acid and alkali metal salts of alkylaryl phosphoric acid.

16. The composition according to claim 14 or 15, wherein the alkali metal salt of the phosphate compound is an alkali metal salt of polyoxyalkylene alkyl ether phosphate.

17. The composition according to any one of claims 14 to 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 of the polyorganosiloxane-containing polymer particle group and at least one component selected from the group consisting of the phosphoric acid compound and its alkali metal salt.

18. A resin composition comprising a group of polyorganosiloxane-containing polymer particles according to any one of claims 1 to 13, and a thermoplastic resin.

19. A resin composition comprising the composition according to any one of claims 14 to 17 and a thermoplastic resin.

20. The resin composition according to claim 18 or 19, 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.

21. A molded article comprising a group of polyorganosiloxane-containing polymer particles according to any one of claims 1 to 13.

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