Composition, resin composition, and molded body

Abstract

Provided are: a molded body having an excellent flexural modulus and colored appearance; and a composition and a resin composition from which a molded body having an excellent flexural modulus and colored appearance can be obtained. A composition according to the present invention contains a polyorganosiloxane-containing polymer (C). The composition contains a polymer soluble in tetrahydrofuran and a polymer insoluble in tetrahydrofuran. The content of a constitutional unit derived from an aromatic vinyl monomer in the polymer soluble in the tetrahydrofuran is at most 3.5 mass% with respect to the total mass of the composition, the composition contains an Fe element, the content of the Fe element per 1 g of the composition is at most 1.58 μg / g, and the mass average particle diameter of the composition is at most 150 nm.

Description

Compositions, resin compositions, and molded articles

[0001] The present invention relates to compositions, resin compositions, and molded articles. This application claims priority based on Japanese Patent Application No. 2025-053105, filed in Japan on March 27, 2025, the contents of which are incorporated herein by reference.

[0002] Rubber-containing polymers, in which vinyl monomers are polymerized onto a rubbery polymer, can be dispersed in a wide variety of resins while maintaining a predetermined rubber particle size and rubber structure, making them suitable for use in resins where impact strength is required. Generally, using rubbery polymers with low elastic modulus and high Poisson's ratio is preferable from the standpoint of improving impact strength. Butadiene rubber and silicone-based rubbers are suitable as rubbery polymers because they have an extremely high Poisson's ratio of 0.5 and a low elastic modulus. Among these, silicone-based rubbers are less prone to hardening and discoloration due to heat and ultraviolet rays compared to butadiene rubber, and have superior durability, making them suitable for use in applications where long-term maintenance of mechanical properties such as flexural modulus is required, such as building materials and automotive components. Polyorganosiloxanes, such as polydimethylsiloxane, are used as silicone-based rubbers.

[0003] However, polyorganosiloxanes are more expensive than butadiene rubber. Furthermore, when polyorganosiloxane-containing polymers are blended with resins that have a higher refractive index than polyorganosiloxanes (e.g., polycarbonate, polymethyl methacrylate, styrene-acrylonitrile copolymer, etc.) and molded into a product, the transparency of the molded product decreases, making it difficult to achieve a colored appearance, especially deep, rich colors.

[0004] Patent documents 1 and 2 describe resin compositions comprising a polymethyl methacrylate resin and a polyorganosiloxane-containing graft copolymer.

[0005] Japanese Patent Publication No. 2000-327880, International Publication No. 2021 / 251496

[0006] However, molded articles obtained using the resin compositions described in Patent Documents 1 and 2 do not necessarily satisfy the desired colored appearance. An object of the present invention is to provide a composition and a resin composition that yield molded articles with excellent flexural modulus and colored appearance. Another object of the present invention is to provide molded articles with excellent flexural modulus and colored appearance.

[0007] The present invention has the following embodiments: [1] A composition comprising a polyorganosiloxane-containing polymer (C), wherein the composition comprises a polymer soluble in tetrahydrofuran and a polymer insoluble in tetrahydrofuran, the content of constituent units derived from aromatic vinyl monomers in the polymer soluble in tetrahydrofuran is 3.5% by mass or less with respect to the total mass of the composition, the composition contains Fe element, the content of Fe element per 1 g of the composition is 1.58 μg / g or less, and the mass-average particle diameter of the composition is 150 nm or less. [2] The composition according to [1], wherein when the content of constituent units derived from aromatic vinyl monomers in the polymer soluble in tetrahydrofuran is α (mass%) with respect to the total mass of the composition, and the content of Fe element per 1 g of the composition is β (μg / g), α / β is 3 or more. [3] The composition of [1] or [2] wherein the polyorganosiloxane-containing polymer (C) comprises a polymer (A) portion containing a polyorganosiloxane (A1) and a first vinyl polymer (A2), and a second vinyl polymer (B) portion. [4] The composition of [3] wherein the content of the polymer (A) portion is 60% by mass or more and 95% by mass or less based on the total mass of the composition. [5] The composition of [3] or [4] wherein the first vinyl polymer (A2) is a polymer of vinyl monomer component (a2), and the vinyl monomer component (a2) contains a (meth)acrylate monomer. [6] The composition of any one of [3] to [5] wherein the second vinyl polymer (B) portion is a polymer of vinyl monomer component (b), and the vinyl monomer component (b) contains a (meth)acrylate monomer and an aromatic vinyl monomer. [7] The composition of [6] wherein the total content of the (meth)acrylate monomer and the aromatic vinyl monomer in the vinyl monomer component (b) is 50% by mass or more with respect to the total mass of the vinyl monomer component (b). [8] The composition of [6] or [7] wherein the vinyl monomer component (b) contains methyl methacrylate, and the content of the methyl methacrylate is 10% by mass or more with respect to the total mass of the vinyl monomer component (b).[9] The composition according to any one of [3] to [8], wherein the polymer (A) moiety 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).

[10] The composition according to any one of [3] to [9], wherein the content of the polyorganosiloxane (A1) is 1% by mass or more and 50% by mass or less based on the total mass of the composition.

[11] The composition according to any one of [3] to [9], wherein the content of the polyorganosiloxane (A1) is 1% by mass or more and 10% by mass or less based on the total mass of the composition.

[12] A resin composition comprising the composition according to any one of [1] to

[11] and a thermoplastic resin other than the composition.

[13] A molded article comprising the resin composition according to

[12] .

[0008] According to the composition of the present invention, a molded article excellent in flexural modulus and colored appearance can be obtained. According to the resin composition of the present invention, a molded article excellent in flexural modulus and colored appearance can be obtained. The molded article of the present invention is excellent in flexural modulus and colored appearance.

[0009] Hereinafter, the present invention will be described in more detail by presenting preferred embodiments of the invention. However, the following description is an example of the embodiments of the present invention, and the present invention is not limited to the following content unless it exceeds the gist of the present invention. In the present specification, the following definitions of terms are adopted. The term "structural unit" means a structural unit derived from a monomer, that is, a structural unit formed by polymerization of a monomer, or a structural unit in which a part of the structural unit is converted into another structure by treating a polymer. A "vinyl monomer" is a compound having a polymerizable double bond. The generic term for acrylate and methacrylate is referred to as "(meth)acrylate". The generic term for acrylic and methacrylic is referred to as "(meth)acrylic". A "molded article" is a molded product obtained by molding the composition or the resin composition of the present invention. In the present specification, "nuclear magnetic resonance analysis" is also referred to as "NMR". A numerical range represented by "~" means a numerical range including the numerical values before and after ~ as the lower limit and the upper limit. The numerical ranges of the content, various physical property values and property values disclosed in the present specification can be combined arbitrarily with the lower limit values and upper limit values to form new numerical ranges.

[0010] [Composition] A composition according to one embodiment of the present invention (hereinafter also referred to as "composition (X)") comprises a polyorganosiloxane-containing polymer (C) (hereinafter also referred to as "polymer (C)"). Composition (X) is a resin additive that is mixed with a thermoplastic resin (hereinafter also referred to as "thermoplastic resin (E)"). Composition (X) is preferably a powdery composition (polymer powder). Composition (X) is particularly incompatible with a polymer of an aromatic vinyl monomer among thermoplastic resins (E), and has an absolute value of difference in refractive index from the aromatic vinyl monomer of 0. When the difference in refractive index in absolute value from a thermoplastic resin having a refractive index difference of 0.01 or more, or a polymer comprising a structural unit derived from an aromatic vinyl monomer (hereinafter also referred to as "polymer (S)") is 0.01 or more in absolute value, it is suitably used when mixed with a thermoplastic resin (hereinafter, these thermoplastic resins are collectively referred to as "thermoplastic resin (E1)"). Based on the total mass of all structural units constituting polymer (S), the proportion of structural units derived from an aromatic vinyl monomer is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and may be 100% by mass.

[0011] Examples of the thermoplastic resin (E1) include acrylic resins, polypropylene resins, and polyethylene resins. Acrylic resins and polypropylene resins are preferred, and acrylic resins are more preferred. That is, composition (X) is more suitably used when mixed with an acrylic resin, a polypropylene resin, or a polyethylene resin, and is particularly suitably used when mixed with an acrylic resin.

[0012] Composition (X) may consist only of polymer (C), or may comprise a component other than polymer (C) (hereinafter also referred to as "other components") in addition to polymer (C). Polymer (C) and other components will be described in detail later.

[0013] It is preferable that composition (X) is insoluble in tetrahydrofuran (THF). That is, it is preferable that composition (X) contains a polymer that is insoluble in tetrahydrofuran. Composition (X) may contain a component that is soluble in THF. That is, a part of composition (X) may be soluble in THF. That is, a polymer that is soluble in tetrahydrofuran may be present in composition (X). It is more preferable that composition (X) contains both a polymer soluble in tetrahydrofuran and a polymer insoluble in tetrahydrofuran. Hereinafter, the portion of composition (X) that is insoluble in THF will also be referred to as the "THF-insoluble portion," and the portion that is soluble in THF will also be referred to as the "THF-soluble portion." Furthermore, "THF-soluble components" refer to the components that leach into THF when a mixture (mixed solution) of composition (X) and 8,900 parts by mass of THF per 100 parts by mass of composition (X) is left to stand at 25°C for 8 hours, and then stirred for 30 minutes with a stirrer (EYELA magnetic stirrer RCN-3D).

[0014] "THF-insoluble matter" In composition (X), the THF-insoluble matter is mainly polymer (C). The ratio of THF-insoluble matter to the total mass of composition (X) 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. If the ratio of THF-insoluble matter is above the lower limit, the dispersibility of composition (X) in thermoplastic resin (E) is better, and the impact strength and appearance of the resulting molded article are better. The ratio of THF-insoluble matter to the total mass of composition (X) may be 100% by mass, less than 100% by mass, or 99% by mass or less. The lower the ratio of THF-insoluble matter, the better the balance between impact strength and colored appearance, and if it is 99% by mass or less, the melt flowability when added to thermoplastic resin (E) is better. That is, the ratio of polymer (C) to the total mass of composition (X) 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 may be 100% by mass, less than 100% by mass, or 99% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, it 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 less than 100% by mass, or 93% by mass or more and 99% by mass or less.

[0015] The THF-insoluble components are measured by performing the following operations (1-1) to (1-5). (1-1): Add 0.5 g of the sample (composition (X)) to 50 mL (44.5 g) of THF, let it stand at 25°C for 8 hours, then stir with a stirrer (EYELA magnetic stirrer RCN-3D) for 30 minutes to dissolve the THF-soluble components in THF and obtain a mixture. (1-2): Place the mixture obtained in (1-1) into a centrifuge tube whose mass has been measured, and centrifuge the liquid containing the THF-insoluble components and the THF-soluble components (supernatant) using a centrifuge (16000 rpm, 4 hours). (1-3): After separating the supernatant containing the THF-soluble components, add fresh THF to the THF-insoluble components and stir, then centrifuge again in the same manner as in (1-2) to wash away the 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 (1). ａｉｓ Calculate the percentage (w). ａｉｓ = (w ｃ１ -w ａｓ ) / wt × 100 ... (1) (In formula (1), "wt" is the mass of the composition (X) used for measurement, and "w ａｓ " is the mass of the centrifuge tube, and "w ｃ１ This represents the mass of the THF-insoluble portion (including the centrifuge tube).

[0016] In composition (X), the THF-soluble component mainly consists of other components and may include aromatic vinyl monomers and polymers (S). The amount of constituent units derived from aromatic vinyl monomers contained in the THF-soluble component is greater than 0% by mass and less than or equal to 3.5% by mass relative to the total mass of composition (X). The amount of constituent units derived from aromatic vinyl monomers contained in the THF-soluble component may be greater than 0% by mass and less than or equal to 3.2% by mass, greater than 0% by mass and less than or equal to 3.0% by mass, greater than 0% by mass and less than or equal to 2.8% by mass, greater than 0% by mass and less than or equal to 2.6% by mass, greater than 0% by mass and less than or equal to 2.4% by mass, greater than 0% by mass and less than or equal to 2.2% by mass, greater than 0% by mass and less than or equal to 2.0% by mass, greater than 0% by mass and less than or equal to 1.8% by mass, greater than 0% by mass and less than or equal to 1.6% by mass, and greater than 0% by mass and less than or equal to 1.4% by mass, relative to the total mass of composition (X). In the present invention, "amount of constituent units derived from aromatic vinyl monomers contained in the THF-soluble portion" means the total amount of aromatic vinyl monomers and constituent units derived from aromatic vinyl monomers constituting the polymer (S) in the THF-soluble portion, relative to the total mass of composition (X).

[0017] As a result of diligent research, the present inventors have discovered that, surprisingly, a molded article with excellent flexural modulus and colored appearance can be obtained when the amount of constituent units derived from aromatic vinyl monomers in the THF-soluble portion of composition (X) is greater than 0% by mass and less than or equal to 3.5% by mass relative to the total mass of composition (X). The reason for obtaining such an effect is not clear, but it is presumed to be as follows: Composition (X) of the present application contains a polymer (C), and the inclusion of polyorganosiloxane in polymer (C) makes it easier to improve the flexural modulus of the molded article. Furthermore, as will be described in detail later, when polymer (C) consists of a polymer (A) portion and a second vinyl polymer (B) portion, the dispersibility of polymer (C) in thermoplastic resin (E) tends to be further improved when the second vinyl polymer (B) contains constituent units derived from aromatic vinyl monomers as a constituent vinyl monomer component (b). On the other hand, unreacted vinyl monomer components (b) that were not used in the polymerization of the second vinyl polymer (B), such as aromatic vinyl monomers and their polymers (other polymers that do not fall under polymer (C)), may leach as THF-soluble components. If the THF-soluble components do not contain constituent units derived from aromatic vinyl monomers, that is, if the amount of constituent units derived from aromatic vinyl monomers in the THF-soluble components is 0% by mass, it means that the vinyl monomer component (b) does not contain aromatic vinyl monomers, or if it does, the proportion is very small. If the amount of constituent units derived from aromatic vinyl monomers in the THF-soluble components is greater than 0% by mass, the dispersibility of polymer (C) tends to be good, and consequently, the colored appearance is less likely to deteriorate. If the amount of constituent units derived from aromatic vinyl monomers in the THF-soluble components is 3.5% by mass or less, the dispersibility of polymer (C) tends to be good, and consequently, the colored appearance is less likely to deteriorate.

[0018] In the composition (X) of the present invention, the amount of constituent units derived from aromatic vinyl monomers contained in the THF-soluble components is 3.5% by mass or less of the total mass of composition (X), which is sufficiently reduced. Therefore, when using composition (X) of the present invention, a molded article with excellent colored appearance can be obtained. Accordingly, as described above, composition (X) can be used in combination with thermoplastic resin (E1).

[0019] The amount of structural units derived from aromatic vinyl monomer contained in the THF-soluble fraction is １ determined by performing 1H-NMR measurement. Specifically, first, THF is distilled off under reduced pressure using a rotary evaporator from the supernatant containing the THF-soluble fraction separated in the above measurement of the ratio of THF-insoluble fraction to obtain a THF-soluble fraction, and the obtained THF-soluble fraction is dissolved in a heavy solvent to prepare a measurement sample. Examples of the heavy solvent include dichloromethane-d ２ , dimethyl sulfoxide-d ６ and the like. The concentration of the measurement sample is not particularly limited, but can usually be about 5% by mass relative to the total mass of the measurement sample. An internal standard substance may be added to the measurement sample. Examples of the internal standard substance include maleic acid and the like.

[0020] Next, １ by multiplying the molar ratio of structural units derived from aromatic vinyl monomer determined by 1H-NMR measurement by the molecular weight of the aromatic vinyl monomer, the total weight of the aromatic vinyl monomer and polymer (S) contained in the THF-soluble fraction is calculated as the amount of structural units derived from aromatic vinyl monomer. Next, the amount of structural units derived from aromatic vinyl monomer is divided by the total weight of structural units other than structural units derived from aromatic vinyl monomer (other structural units) contained in the THF-soluble fraction, which are similarly measured and calculated, and further multiplied by the ratio of the THF-soluble fraction (100-w ａｉｓ ), thereby obtaining the amount of structural units derived from aromatic vinyl monomer contained in 100% by mass of the composition (X).

[0021] The amount of constituent units derived from aromatic vinyl monomers in the THF-soluble components can be adjusted, for example, by the composition of the vinyl monomer component (b) described later, the amount of polymerization initiator and chain transfer agent used when polymerizing the vinyl monomer component (b), etc. Specifically, the less aromatic vinyl monomers contained in the vinyl monomer component (b), the less chain transfer agent is used, or the higher the proportion of polyfunctional monomers in the vinyl monomer component (b), the less the amount of constituent units derived from aromatic vinyl monomers in the THF-soluble components of the composition (X) tends to be. From the viewpoint of improving the colored appearance due to the effect of improving the dispersibility of composition (X) in the thermoplastic resin (E), it is preferable to include aromatic vinyl monomers as vinyl monomer component (b). By including aromatic vinyl monomers as vinyl monomer component (b), it is important to suppress the elution of aromatic vinyl monomer components into the THF-soluble components while still including aromatic vinyl monomers as vinyl monomer component (b).

[0022] The weight-average molecular weight of the THF-soluble component is preferably 20,000 or more, more preferably 50,000 or more, while it is preferably 1,000,000 or less, more preferably 800,000 or less, even more preferably 650,000 or less, and particularly preferably 550,000 or less. It may also be 500,000 or less, 350,000 or less, 200,000 or less, or 150,000 or less. The above upper and lower limits can be combined in any way. For example, it may be between 20,000 and 1,000,000, between 20,000 and 800,000, between 20,000 and 650,000, between 20,000 and 550,000, between 20,000 and 500,000, between 20,000 and 350,000, between 20,000 and 200,000, between 20,000 and 150,000, between 50,000 and 1,000,000, between 50,000 and 800,000, between 50,000 and 650,000, between 50,000 and 550,000, between 50,000 and 500,000, between 50,000 and 350,000, between 50,000 and 200,000, or between 50,000 and 150,000. If the weight-average molecular weight of the THF-soluble component is within the range of the upper and lower limits, the composition (X) will have excellent dispersibility in the thermoplastic resin (E) and the resulting molded article will have excellent appearance. In particular, if the weight-average molecular weight of the THF-soluble components is between 50,000 and 150,000, the dispersibility of composition (X) in thermoplastic resin (E) is especially good, and the appearance of the resulting molded article is excellent under a wide range of molding conditions, including low levels of kneading.

[0023] The weight-average molecular weight of the THF-soluble components is measured by performing the following operations (2-1) to (2-3). (2-1): From the supernatant containing the THF-soluble components separated by the measurement of the ratio of THF-insoluble components described above, THF is removed under reduced pressure using a rotary evaporator to obtain the THF-soluble components. (2-2): The THF-soluble components obtained in (2-1) are dissolved again in THF to a sample concentration of 0.1 to 0.3 mass% to obtain a THF solution of the THF-soluble components. (2-3): The THF solution of the THF-soluble components obtained in (2-2) is subjected to gel permeation chromatography (GPC) measurement, 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.

[0024] The weight-average molecular weight of the THF-soluble components can be adjusted by the amount of initiator and reducing agent, polymerization temperature, and use of chain transfer agents when polymerizing the vinyl monomer component (b) described below. For example, increasing the amount of initiator and reducing agent or raising the polymerization temperature to enhance radical generation, or accelerating the chain transfer reaction by adding and increasing the amount of chain transfer agents, will decrease the weight-average molecular weight of the THF-soluble components.

[0025] "Measurement of Fe element content" Composition (X) contains Fe element, and the Fe element content per gram of composition (X) is 1.58 μg / g or less. The Fe element content per gram of composition (X) may be 1.50 μg / g or less, 1.30 μg / g or less, 1.00 μg / g or less, 0.95 μg / g or less, 0.90 μg / g or less, 0.85 μg / g or less, 0.80 μg / g or less, 0.75 μg / g or less, 0.70 μg / g or less, 0.65 μg / g or less, 0.60 μg / g or less, or 0.55 μg / g or less. On the other hand, it may be 0.01 μg / g or more, 0.05 μg / g or more, 0.10 μg / g or more, 0.15 μg / g or more, or 0.20 μg / g or more. The above upper and lower limits can be combined in any way. For example, it may be 0.01 to 1.58 μg / g, 0.01 to 1.50 μg / g, 0.01 to 1.30 μg / g, 0.01 to 1.00 μg / g, 0.01 to 0.95 μg / g, 0.01 to 0.90 μg / g, 0.01 to 0.85 μg / g, 0.01 to 0.80 μg / g, 0.01 to 0.75 μg / g, 0.01 to 0.70 μg / g, 0.01 to 0.65 μg / g, 0.01 to 0.60 μg / g, 0.01 to 0.55 μg / g, 0.05 to 1.58 μg / g, 0.05 to 1.5 It may be 0 μg / g, 0.05 to 1.30 μg / g, 0.05 to 1.00 μg / g, 0.05 to 0.95 μg / g, 0.05 to 0.90 μg / g, 0.05 to 0.85 μg / g, 0.05 to 0.80 μg / g, 0.05 to 0.75 μg / g, 0.05 to 0.70 μg / g, 0.05 to 0.65 μg / g, 0.05 to 0.60 μg / g, 0.05 to 0.55 μg / g, 0.10 to 1.58 μg / g, 0.10 to 1.50 μg / g, 0.10 to 1.30 μg / g,It may be 0.10 to 1.00 μg / g, 0.10 to 0.95 μg / g, 0.10 to 0.90 μg / g, 0.10 to 0.85 μg / g, 0.10 to 0.80 μg / g, 0.10 to 0.75 μg / g, 0.10 to 0.70 μg / g, 0.10 to 0.65 μg / g, or 0.10 to 0.60 μg / g. It may be 0.10 to 0.55 μg / g, 0.15 to 1.58 μg / g, 0.15 to 1.50 μg / g, 0.15 to 1.30 μg / g, 0.15 to 1.00 μg / g, 0.15 to 0.95 μg / g, 0.15 to 0.90 μg / g, 0.15 to 0.85 μg / g, or 0.15 to 0.80 μg / g. It may be 0.15 to 0.75 μg / g, 0.15 to 0.70 μg / g, 0.15 to 0.65 μg / g, 0.15 to 0.60 μg / g, 0.15 to 0.55 μg / g, 0.20 to 1.58 μg / g, 0.20 to 1.50 μg / g, 0.20 to 1.30 μg / g, or 0.20 to 1.00 μg / g. It may be 0.20 to 0.95 μg / g, 0.20 to 0.90 μg / g, 0.20 to 0.85 μg / g, 0.20 to 0.80 μg / g, 0.20 to 0.75 μg / g, 0.20 to 0.70 μg / g, 0.20 to 0.65 μg / g, 0.20 to 0.60 μg / g, or 0.20 to 0.55 μg / g.

[0026] As a result of diligent research, the inventors have found that when the Fe element content per gram of composition (X) is greater than 0 μg / g and less than or equal to 1.58 μg / g, deterioration of appearance can be suppressed even when high heat and retention conditions occur during molding. The reason for this effect is not entirely clear, but it is presumed to be as follows.

[0027] In emulsion polymerization, the polymerization reaction first proceeds in water. As the degree of polymerization increases, the hydrophobicity also increases, and the reactants that can no longer remain in water move to micelles formed by the emulsifier, where the reaction continues to proceed. To obtain a copolymer, the copolymer composition can be adjusted by appropriately adjusting the dispersion state of each monomer component and the polymerization rate during polymerization. As the scale increases, the stirring efficiency decreases, making it easy for each monomer component to be unevenly distributed. Furthermore, if radical generation becomes excessive, certain monomer components will polymerize unevenly, resulting in a difference (composition difference) between the initial composition and the actual copolymerized composition. Composition differences can cause the acquisition of insufficient physical properties in practical applications, such as the occurrence of unexpected discoloration, decreased compatibility with the resin, and ultimately deterioration of appearance and reduced impact strength due to decreased dispersibility.

[0028] By keeping the amount of Fe element in composition (X) below the upper limit of the above range, the amount of radical generation becomes appropriate, reducing the compositional difference and preventing a decrease in physical properties. On the other hand, when the amount of Fe element in composition (X) is 0 μg / g, that is, when virtually no iron compound is used in the manufacturing process, the polymerization rate decreases significantly, making it impractical for actual manufacturing. For the above reasons, it is necessary to use an iron compound such that the amount of Fe element in composition (X) falls within the above range.

[0029] In composition (X), when the amount of constituent units derived from aromatic vinyl monomers in the tetrahydrofuran-soluble polymer is α (mass%), and the amount of element Fe per 1 g of composition (X) is β (μg / g), it is preferable that α / β is 3.0 or more, may be 3.5 or more, may be 4.0 or more, may be 4.5 or more, may be 5.5 or more, on the other hand, may be 100 or less, may be 50 or less, may be 40 or less, may be 30 or less, may be 10 or less, may be 9.5 or less, may be 9.0 or less, may be 8.5 or less, may be 8.0 or less, may be 7.5 or less, may be 7.0 or less, and may be 6.5 or less. The above upper and lower limits can be combined arbitrarily.For example, it may be 3.0 to 100, 3.0 to 50, 3.0 to 40, 3.0 to 30, 3.0 to 10, 3.0 to 9.5, 3.0 to 9.0, 3.0 to 8.5, 3.0 to 8.0, 3.0 to 7.5, 3.0 to 7.0, 3.0 to 6.5, 3.5 to 100, 3.5 to 50, 3.5 to 40. It may be 3.5 to 30, 3.5 to 10, 3.5 to 9.5, 3.5 to 9.0, 3.5 to 8.5, 3.5 to 8.0, 3.5 to 7.5, 3.5 to 7.0, 3.5 to 6.5, 4.0 to 100, 4.0 to 50, 4.0 to 40, 4.0 to 30, 4.0 to 10, 4.0 to 9.5, It may be 4.0 to 9.0, it may be 4.0 to 8.5, it may be 4.0 to 8.0, it may be 4.0 to 7.5, it may be 4.0 to 7.0, it may be 4.0 to 6.5, it may be 4.5 to 100, it may be 4.5 to 50, it may be 4.5 to 40, it may be 4.5 to 30, it may be 4.5 to 10, it may be 4.5 to 9.5, it may be 4.5 to 9.0, it may be 4.5 to 8.5, it may be 4.5 to 8.0 It may be 4.5 to 7.5, 4.5 to 7.0, 4.5 to 6.5, 5.5 to 100, 5.5 to 50, 5.5 to 40, 5.5 to 30, 5.5 to 10, 5.5 to 9.5, 5.5 to 9.0, 5.5 to 8.5, 5.5 to 8.0, 5.5 to 7.5, 5.5 to 7.0, and 5.5 to 6.5.

[0030] "Mass-average particle diameter" The mass-average particle diameter of composition (X) may be 10 nm or more, 30 nm or more, 50 nm or more, 70 nm or more, 80 nm or more, 85 nm or more, 90 nm or more, 95 nm or more, or 100 nm or more. On the other hand, it may be 150 nm or less, 148 nm or less, 145 nm or less, 143 nm or less, 140 nm or less, or 138 nm or less. The above upper and lower limits can be combined in any way.For example, it may be 10-150 nm, 10-148 nm, 10-145 nm, 10-143 nm, 10-140 nm, 10-138 nm, 30-150 nm, 30-148 nm, 30-145 nm, 30-143 nm, 30-140 nm, 30-138 nm, 50-150 nm, 50-148 It may be nm, it may be 50-145 nm, it may be 50-143 nm, it may be 50-140 nm, it may be 50-138 nm, it may be 70-150 nm, it may be 70-148 nm, it may be 70-145 nm, it may be 70-143 nm, it may be 70-140 nm, it may be 70-138 nm, it may be 80-150 nm, it may be 80-148 nm, it may be 80-145 nm, 8 It may be 0-143 nm, 80-140 nm, 80-138 nm, 85-150 nm, 85-148 nm, 85-145 nm, 85-143 nm, 85-140 nm, 85-138 nm, 90-150 nm, 90-148 nm, 90-145 nm, 90-143 nm, and 90-140 nm. The particle size may be 90-138 nm, 95-150 nm, 95-148 nm, 95-145 nm, 95-143 nm, 95-140 nm, 95-138 nm, 100-150 nm, 100-148 nm, 100-145 nm, 100-143 nm, 100-140 nm, or 100-138 nm. If the mass-average particle size of composition (X) is greater than or equal to the lower limit, the impact strength of the resulting molded article will be superior, and if it is less than or equal to the upper limit, the colored appearance of the resulting molded article will be superior. Furthermore, even when flame retardancy is required for the molded article, the flame retardancy of the molded article will be superior if the mass-average particle size is less than or equal to the upper limit.

[0031] The mass-average particle size of composition (X) is measured by the following method: A sample of latex from composition (X) diluted with deionized water to a concentration of approximately 3% is used, and the mass-based particle size distribution is measured using a capillary particle size analyzer (for example, the "CHDF2000" product manufactured by MATEC, Inc., USA), and the median diameter is taken as the mass-average particle size.

[0032] Particle size distribution measurements can be performed under the following standard conditions recommended by MATEC: • Cartridge: Dedicated capillary cartridge for particle separation (product name: C-202), • Carrier solution: Dedicated carrier solution (product name: 2XGR500), • Acidity of carrier solution: Neutral, • Flow rate of carrier solution: 1.4 mL / min, • Pressure of carrier solution: Approximately 4,000 psi (2,600 kPa), • Measurement temperature: 35°C, • Sample volume: 0.1 mL. Additionally, 12 types of monodisperse polystyrene with known particle sizes, manufactured by DUKE, USA, with particle sizes ranging from 40 to 800 nm, are used as standard particle size materials.

[0033] The mass-average particle size of composition (X) can be adjusted, for example, by the amount of emulsifier when polymer (C) is produced by emulsion polymerization.

[0034] "Polyorganosiloxane-containing polymer (C)" Polymer (C) preferably contains constituent units derived from aromatic vinyl monomers from the viewpoint of improving impact strength. The ratio of constituent units derived from aromatic vinyl monomers to the total mass of all constituent units of polymer (C) is preferably 15% by mass or more, more preferably 16% by mass or more, even more preferably 16.5% by mass or more, while preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, it may be 15% by mass or more and 30% by mass or less, 15% by mass or more and 25% by mass or less, 15% by mass or more and 20% by mass or less, 16% by mass or more and 30% by mass or less, 16% by mass or more and 25% by mass or less, 16% by mass or more and 20% by mass or less, 16.5% by mass or more and 30% by mass or less, 16.5% by mass or more and 25% by mass or less, and 16.5% by mass or more and 20% by mass or less. If the ratio of constituent units derived from aromatic vinyl monomers is equal to or greater than the lower limit, the impact strength of the molded article obtained by blending composition (X) with thermoplastic resin (E) will be higher. If the ratio of constituent units derived from aromatic vinyl monomers is equal to or less than the upper limit, the appearance of the molded article obtained by blending composition (X) with thermoplastic resin (E), particularly thermoplastic resin (E1), will be better.

[0035] The polymer (C) preferably consists of a polymer (A) portion and a second vinyl polymer (B) portion (hereinafter also referred to as the "polymer (B) portion"). It is preferable that at least one of the polymer (A) portion and the polymer (B) portion contains structural units derived from aromatic vinyl monomers. In particular, from the viewpoint of improving the dispersibility of composition (X) in thermoplastic resin (E), it is preferable that at least the polymer (B) portion contains structural units derived from aromatic vinyl monomers.

[0036] The ratio of the polymer (A) portion to the total mass of composition (X) 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. The above upper and lower limits can be arbitrarily combined. For example, it may be 60% by mass or more and 95% by mass or less, 60% by mass or more and 90% by mass or less, 60% by mass or more and 85% by mass or less, 65% by mass or more and 95% by mass or less, 65% by mass or more and 90% by mass or less, and 65% by mass or more and 85% by mass or less. If the ratio of the polymer (A) portion 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 composition (X) in the thermoplastic resin (E) is better, and the appearance of the resulting molded article is better.

[0037] The ratio of the polymer (B) portion to the total mass of composition (X) 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. The above upper and lower limits can be arbitrarily combined. For example, it may be 5% by mass or more and 40% by mass or less, 5% by mass or more and 35% by mass or less, 10% by mass or more and 40% by mass or less, 10% by mass or more and 35% by mass or less, 15% by mass or more and 40% by mass or less, and 15% by mass or more and 35% by mass or less. If the ratio of the polymer (B) portion is above the lower limit, the dispersibility of composition (X) in the thermoplastic resin (E) is better and the appearance of the resulting molded article is better, and if it is below the upper limit, the impact strength of the molded article is better.

[0038] Polymer (C) may be a polymer in which polymer (A) and polymer (B) are covalently bonded, or it may be a polymer in which polymer (A) and polymer (B) are not covalently bonded. An example of a polymer in which polymer (A) and polymer (B) are covalently bonded is a block copolymer having polymer (A) and polymer (B). An example of a polymer in which polymer (A) and polymer (B) are not covalently bonded is a polymer in which polymer (B) is enclosed or enclosed by polymer (A). Specifically, an example of a polymer having a core-shell structure is an example, in which one of polymer (A) and polymer (B) is contained in a core and the other in a shell. A "core-shell structure" is a structure in which a part called the core is contained in a part called the shell.

[0039] Among these, polymer (C) is preferably a polymer having a core-shell structure, in which polymer (B) constitutes the shell portion of the core-shell structure and polymer (A) constitutes the core portion of the core-shell structure. The following describes in detail a preferred form of polymer (C) having a core-shell structure in which polymer (B) constitutes the shell portion of the core-shell structure and polymer (A) constitutes the core portion of the core-shell structure, as a representative example.

[0040] <Polymer (A) portion> The polymer (A) portion may include the polyorganosiloxane (A1) and the first vinyl polymer (A2) shown below (hereinafter also referred to as "vinyl polymer (A2)"). Preferably, the polymer (A) portion is a polymer obtained by polymerizing the vinyl monomer component (a2) constituting the vinyl polymer (A2) in the presence of a latex containing polyorganosiloxane (A1). In this invention, the polymer (A) portion is also simply referred to as "polymer (A)".

[0041] The mass ratio represented by polyorganosiloxane (A1) / 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.

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

[0043] Examples of organosiloxanes include linear organosiloxanes, alkoxysilane compounds, and cyclic organosiloxanes. These can be used individually or in combination of two or more. Among these, alkoxysilane compounds and cyclic organosiloxanes are preferred, and cyclic organosiloxanes are particularly preferred because they yield a composition (X) containing a polymer (C) that can increase the flexural modulus and impact strength of the molded article, and also because they have high polymerization stability and a high polymerization rate.

[0044] As the alkoxysilane compound, bifunctional alkoxysilane compounds are preferred, for example, dimethyldimethoxysilane, dimethyldiethoxysilane, diethoxydiethylsilane, dipropoxydimethylsilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, and methylphenyldiethoxysilane. These can be used individually or in combination of two or more. Among these, dimethyldimethoxysilane, dimethyldiethoxysilane, diethoxydiethylsilane, and diphenyldimethoxysilane are more preferred, dimethyldimethoxysilane, dimethyldiethoxysilane, and diethoxydiethylsilane are even more preferred, dimethyldimethoxysilane and dimethyldiethoxysilane are particularly preferred, and dimethyldimethoxysilane is the most preferred.

[0045] As cyclic organosiloxanes, cyclic organosiloxanes 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, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane are preferred because they allow for easy control of the particle size distribution, hexamethylcyclotrisiloxane and octamethylcyclotetrasiloxane are more preferred, and octamethylcyclotetrasiloxane is even more preferred.

[0046] As the organosiloxane, at least one selected from the group consisting of cyclic dimethylsiloxanes and difunctional dialkyldialkoxysilane compounds is preferred, since it yields a composition (X) containing a polymer (C) that can further increase the flexural modulus and impact strength of the molded article.

[0047] Cyclic dimethylsiloxanes are cyclic siloxanes having two methyl groups attached to a silicon atom. Examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and tetradecamethylcycloheptasiloxane. These can be used individually or in combination of two or more. Among these, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane are more preferred, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane are even more preferred, hexamethylcyclotrisiloxane and octamethylcyclotetrasiloxane are particularly preferred, and octamethylcyclotetrasiloxane is the most preferred.

[0048] A bifunctional dialkyldialkoxysilane compound is a silane compound having two alkoxy groups and two alkyl groups attached to a silicon atom. Examples include dimethyldimethoxysilane, dimethyldiethoxysilane, diethoxydiethylsilane, dipropoxydimethylsilane, and diphenyldimethoxysilane. These can be used individually or in combination of two or more. Among these, dimethyldimethoxysilane, dimethyldiethoxysilane, diethoxydiethylsilane, and diphenyldimethoxysilane are more preferred, dimethyldimethoxysilane, dimethyldiethoxysilane, and diethoxydiethylsilane are even more preferred, dimethyldimethoxysilane and dimethyldiethoxysilane are particularly preferred, and dimethyldimethoxysilane is the most preferred.

[0049] The ratio of organosiloxane to the total mass of the organosiloxane mixture for obtaining organosiloxane (A1) is preferably 90.0% by mass or more, more preferably 95.0% by mass or more, while it may be 100% by mass, 99.5% by mass or less, or 99.0% by mass or less. The above upper and lower limits can be arbitrarily combined. For example, it may be 90.0 to 100% by mass, 90.0 to 99.5% by mass, 90.0 to 99.0% by mass, 95.0 to 100% by mass, 95.0 to 99.5% by mass, or 95.0 to 99.0% by mass. If the ratio of organosiloxane is above the lower limit, the flexural modulus and impact strength of the molded article obtained by blending composition (X) with thermoplastic resin (E) can be further improved.

[0050] As siloxane-based crosslinking agents, those having a siloxy group (-Si-O-) are preferred, and examples include trifunctional or tetrafunctional silane-based crosslinking agents such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, and tetrabutoxysilane. These can be used individually or in combination of two or more. Among these, the tetrafunctional crosslinking agents tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, and tetrabutoxysilane are preferred, with tetraethoxysilane being more preferred.

[0051] The ratio of the siloxane-based crosslinking agent to the total 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. If the ratio of the siloxane-based crosslinking agent is 10% by mass or less, a composition (X) containing a polymer (C) that can improve the flexural modulus and impact strength of the molded article can be obtained.

[0052] Siloxane cross-agents are those that have a siloxy group and functional groups that can polymerize with vinyl monomers. Examples of siloxane cross-agents include siloxanes represented by the following formula (I): R-Si(R １ ) ｎ (OR ２ ) （３－ｎ） ... (I) (In equation (I), R １ R 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). ) CH ２ = C(R ３ )-COO-(CH ２ ) ｐ -...(I-1) CH ２ = C(R ４ )-C ６ H ４ -...(I-2) CH ２ =CH-...(I-3) HS-(CH２ ) ｐ - ... (I-4) In these equations, R ３ and R ４ Each independently represents a hydrogen atom or a methyl group, p is an integer from 1 to 6, and -C ６ H ４ The dash (-) indicates a phenylene group.

[0053] 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, and δ-methacryloyloxybutyldiethoxymethylsilane. Among these, β-methacryloyloxyethyl dimethoxymethylsilane, γ-methacryloyloxypropyl methoxydimethylsilane, γ-methacryloyloxypropyl dimethoxymethylsilane, and γ-methacryloyloxypropyl trimethoxysilane are more preferred, γ-methacryloyloxypropyl methoxydimethylsilane, γ-methacryloyloxypropyl dimethoxymethylsilane, and γ-methacryloyloxypropyl trimethoxysilane are even more preferred, γ-methacryloyloxypropyl methoxydimethylsilane and γ-methacryloyloxypropyl dimethoxymethylsilane are particularly preferred, and γ-methacryloyloxypropyl dimethoxymethylsilane is the most preferred.

[0054] 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 the functional group represented by formula (I-3) include vinyltrimethoxysilane and vinyltriethoxysilane.

[0055] Examples of functional groups represented by formula (I-4) include mercaptoalkyl groups. Examples of siloxanes having this group include γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropylmethoxydimethylsilane, γ-mercaptopropyldiethoxymethylsilane, γ-mercaptopropylethoxydimethylsilane, and γ-mercaptopropyltrimethoxysilane. Among these, γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropylmethoxydimethylsilane, γ-mercaptopropyldiethoxymethylsilane, and γ-mercaptopropylethoxydimethylsilane are more preferred, γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropylmethoxydimethylsilane, and γ-mercaptopropyldiethoxymethylsilane are even more preferred, γ-mercaptopropyldimethoxymethylsilane and γ-mercaptopropylmethoxydimethylsilane are particularly preferred, and γ-mercaptopropyldimethoxymethylsilane is the most preferred.

[0056] Siloxane cross-agents can be used individually or in combination of two or more. Among the siloxane cross-agents, γ-methacryloyloxypropyldimethoxymethylsilane is preferred because it readily forms a sea-island structure when compounded with polyorganosiloxane (A1) and vinyl polymer (A2).

[0057] When the organosiloxane mixture contains a siloxane cross-agent, the ratio of the siloxane cross-agent to the total mass of the organosiloxane mixture is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.5% by mass or more, while preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less. The above upper and lower limits can be arbitrarily combined. For example, it may be 0.05% by mass or more and 20% by mass or less, 0.05% by mass or more and 10% by mass or less, 0.05% by mass or more and 5% by mass or less, 0.1% by mass or more and 20% by mass or less, 0.1% by mass or more and 10% by mass or less, 0.1% by mass or more and 5% by mass or less, 0.5% by mass or more and 20% by mass or less, 0.5% by mass or more and 10% by mass or less, and 0.5% by mass or more and 5% by mass or less. If the ratio of the siloxane cross-agent is within the range of the upper and lower limits, a sufficient covalent bond can be formed between the polyorganosiloxane (A1) and the vinyl polymer (A2), and a composition (X) containing a polymer (C) with good flexural modulus and impact strength can be obtained.

[0058] The mass-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 130 nm or less, and more preferably 100 nm or less. The above upper and lower limits can be combined arbitrarily. For example, it may be 1 nm to 130 nm, 1 nm to 100 nm, 10 nm to 130 nm, 10 nm to 100 nm, 30 nm to 130 nm, or 30 nm to 100 nm. If the mass-average particle diameter of polyorganosiloxane (A1) is within the range of the above upper and lower limits, it is easy to adjust the mass-average particle diameter of composition (X) to within the range of the above preferred upper and lower limits.

[0059] 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 or less. If Dw / Dn is within the range of the upper and lower limits, the colorability of the resin composition containing composition (X) and thermoplastic resin (E) is better, and the colored appearance of the molded article using the resin composition is better.

[0060] The method for measuring the mass-average particle size (Dw) of polyorganosiloxane (A1) is the same as the method for measuring the mass-average particle size of composition (X) described above. The method for measuring the number-average particle size (Dn) of polyorganosiloxane (A1) is the same as the method for measuring the mass-average particle size of composition (X) described above, except that a number-based particle size distribution is measured instead of a mass-based particle size distribution. That is, a sample of polyorganosiloxane (A1) latex diluted to a concentration of approximately 3% with deionized water is used, and the number-based particle size distribution is measured using a capillary particle size analyzer (for example, the "CHDF2000" particle size analyzer manufactured by MATEC, Inc., USA), and the median diameter is taken as the number-average particle size.

[0061] <<Method for Producing Polyorganosiloxane (A1)>> There are no particular restrictions on the method for producing polyorganosiloxane (A1), and for example, the following method 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-closing 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 polyorganosiloxane latex. In the following description of the method, the case in which an "organosiloxane mixture" is used as the raw material for polymerization is described, but the same manufacturing process can be applied when "organosiloxane" is used.

[0062] 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.

[0063] 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.

[0064] 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 by dropping an emulsion of organosiloxane mixture into a high-temperature acid catalyst aqueous solution at a constant rate.

[0065] 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.

[0066] 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.

[0067] 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 alkylbenzene sulfonate, sodium alkyl diphenyl ether disulfonate, sodium alkyl sulfate, sodium polyoxyethylene alkyl sulfate, and sodium polyoxyethylene nonylphenyl ether sulfate. Examples of nonionic emulsifiers include polyoxyethylene alkyl ether, polyoxyethylene alkylene alkyl ether, polyoxyethylene distyrenated phenyl ether, polyoxyethylene tripenzylphenyl ether, and polyoxyethylene polyoxypropylene glycol. These emulsifiers can be used individually or in combination of two or more.

[0068] 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.

[0069] 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).

[0070] 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 above the lower limit, the organosiloxane mixture can be polymerized in a short time. If the amount of acid catalyst used is below the upper limit, the heat discoloration resistance and surface appearance of the molded article are better.

[0071] 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.

[0072] 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.

[0073] <<Ratio of Polyorganosiloxane (A1)>> The ratio of polyorganosiloxane (A1) to the total mass of composition (X) is preferably 50% by mass or less, more preferably 40% by mass or less, more preferably 30% by mass or less, more preferably 20% by mass or less, more preferably 10% by mass or less, more 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. The above upper and lower limits can be combined arbitrarily. For example, it may be 1 to 50% by mass, 1 to 40% by mass, 1 to 30% by mass, 1 to 20% by mass, 1 to 10% by mass, or 1 to 6% by mass.

[0074] (First 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 components (a2) that constitute vinyl polymer (A2) consist of one or more vinyl monomers.

[0075] From the viewpoint of impact strength of the molded article, the vinyl monomer component (a2) preferably contains a (meth)acrylate monomer (hereinafter also referred to as "monomer (a2-1)"). In addition to monomer (a2-1), vinyl monomer component (a2) may further contain at least one selected from the group consisting of a monofunctional monomer that can copolymerize with monomer (a2-1) (hereinafter also referred to as "monomer (a2-2)") and a polyfunctional monomer 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 composition (X) within the above-mentioned range, vinyl monomer component (a2) preferably contains monomer (a2-1) and monomer (a2-3).

[0076] 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, it is preferable to include 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 n-butyl acrylate, as this results in better impact strength of the resulting molded article. These monomers (a2-1) can be used individually or in combination of two or more.

[0077] Examples of monomers (a2-2) include aromatic vinyl monomers such as 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; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; and various vinyl monomers such as (meth)acrylic group-modified silicones. Among these, styrene, alkyl-substituted styrene, acrylonitrile, and acrylic-modified silicone are more preferred, styrene, alkyl-substituted styrene, and acrylic-modified silicone are even more preferred, styrene and alkyl-substituted styrene are particularly preferred, and styrene is the most preferred. These monomers (a2-2) can be used individually or in combination of two or more.

[0078] 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, and triallyl trimellitate. Among these, at least one selected from the group consisting of allyl methacrylate, triallyl cyanurate, and triallyl isocyanurate is preferred, and allyl methacrylate is more preferred, as it results in better impact strength of the resulting molded article. These monomers (a2-3) can be used individually or in combination of two or more.

[0079] From the viewpoint of impact strength of the molded article, the ratio of monomer (a2-1) to the total 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 the total mass of vinyl monomer component (a2) may be 100% by mass, but is preferably 99.9% by mass or less. The above upper and lower limits can be arbitrarily combined. For example, it may be 60% by mass or more and 100% by mass or less, 60% by mass or more and 99.9% by mass or less, 70% by mass or more and 100% by mass or less, 70% by mass or more and 99.9% by mass or less, 80% by mass or more and 100% by mass or less, 80% by mass or more and 99.9% by mass or less, 90% by mass or more and 100% by mass or less, and 90% by mass or more and 99.9% by mass or less.

[0080] The ratio of monomer (a2-2) to the total 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.

[0081] The ratio of monomer (a2-3) to the total mass of vinyl monomer component (a2) 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 the total 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 improving the colored appearance of the molded article, the ratio of monomer (a2-3) to the total 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. From the viewpoint of balancing the melt fluidity during molding with the colored appearance and impact strength of the molded article, the ratio of monomer (a2-3) to the total 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 0.4% by mass or more and 2.5% by mass or less.

[0082] (Manufacturing of Polymer (A) Portion) The method for manufacturing the polymer (A) portion 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.

[0083] 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; (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.

[0084] As a method for producing the polymer (A) portion, among the above, a method is preferred in which the impact strength of the molded article is superior, and the entire amount of the vinyl monomer component (a2) is added to a latex containing polyorganosiloxane (A1) under conditions in which polymerization has not started, impregnating the particles of polyorganosiloxane (A1), and then polymerization is performed.

[0085] As a method for producing the polymer (A) portion, a method comprising the following steps 1 to 3 is particularly preferred.

[0086] <<Step 1>> A latex of polyorganosiloxane (A1) is produced under arbitrary conditions. The latex of polyorganosiloxane (A1) can be produced by the method described above. In this case, it is preferable that polyorganosiloxane (A1) consists of an organosiloxane and a siloxane-based cross-agent.

[0087] <<Step 2>> The entire amount of vinyl monomer component (a2) and a radical polymerization initiator are added to the polyorganosiloxane (A1) latex obtained in Step 1 under conditions that prevent polymerization of vinyl monomer component (a2) from starting, thereby impregnating the polyorganosiloxane (A1) particles. At this time, adding the entire amount of vinyl monomer component (a2) results in superior impact strength of the molded product.

[0088] When the vinyl monomer component (a2) contains multiple types of vinyl monomers, for example, when 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 add it mixed with monomer (a2-1) or / and monomer (a2-2) from the viewpoint of obtaining an appropriate crosslinking structure.

[0089] 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.

[0090] Examples of azo compounds include 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); and 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.

[0091] When an azo compound is used as a radical polymerization initiator, the amount of the azo compound used is preferably 0.01 parts by mass or more per 100 parts by mass of vinyl monomer component (a2), while preferably 3 parts by mass or less, more preferably 1 part by mass or less, and even more preferably 0.5 parts by mass or less. The above upper and lower limits can be combined arbitrarily. For example, it may be 0.01 parts by mass or more and 3 parts by mass or less, 0.01 parts by mass or more and 1 part by mass or less, or 0.01 parts by mass or more and 0.5 parts by mass or less. By keeping the amount of the azo compound used within the above upper and lower limits, it is possible to suppress an excessively high polymerization rate, prevent the polymer from becoming low molecular weight and the resulting liberation from polymer (A), and thus make it easier to obtain a polymer as designed.

[0092] Examples of peroxides include inorganic peroxides such as hydrogen peroxide, potassium persulfate, and ammonium persulfate; and 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.

[0093] When using a peroxide as a radical polymerization initiator, the amount of peroxide used is preferably 0.01 parts by mass or more per 100 parts by mass of vinyl monomer component (a2), while preferably 1 part by mass or less, more preferably 0.8 parts by mass or less, even more preferably 0.5 parts by mass or less, and particularly preferably 0.2 parts by mass or less. The above upper and lower limits can be combined arbitrarily. For example, it may be 0.01 parts by mass or more and 1 part by mass or less, 0.01 parts by mass or more and 0.8 parts by mass or less, 0.01 parts by mass or more and 0.5 parts by mass or less, or 0.01 parts by mass or more and 0.2 parts by mass or less. By keeping the amount of peroxide used within the above upper and lower limits, it is possible to suppress an excessively high polymerization rate, prevent the polymer from becoming low molecular weight and the resulting liberation from polymer (A), and thus make it easier to obtain a polymer as designed.

[0094] 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.

[0095] When using peroxides as radical polymerization initiators, reducing agents can be used in combination to promote the decomposition of the peroxides.

[0096] Examples of reducing agents include sulfur compounds such as sulfite, hydrogen sulfite, alkali metal bisulfite, acetone bisulfite, alkali metal disulfite, metabisulfite 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 sulfoxylate and its salts, hydroxylamine, hydroxylamine hydrosulfate, hydroxylammonium salt, polyamine and dimethylaniline; reducing sugars such as sorbose, fructose, glucose, lactose and dextrose; and ene diols such as ascorbic acid and isoascorbic acid. Examples of "salts" include sodium ions, potassium ions, ammonium ions and zinc ions.

[0097] Furthermore, sulfates, nitrates, acetates, carbonates, and chlorides of transition metals located in groups 3 through 11 of the periodic table are also useful as reducing agents. Examples of transition metals include Ce from group 3, Ti from group 4, V from group 5, Cr and Mo from group 6, Mn from group 7, Fe from group 8, Co from group 9, Ni from group 10, and Cu and Ag from group 11.

[0098] 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.

[0099] 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, and even more preferably 0.6 molar equivalents or less. On the other hand, it may be 0 molar equivalents, 0.01 molar equivalents or more, 0.05 molar equivalents or more, or 0.10 molar equivalents or more. The above upper and lower limits can be combined arbitrarily. For example, the amount may be 0 to 2.0 molar equivalents, 0 to 1.0 molar equivalents, 0 to 0.6 molar equivalents, 0.01 to 2.0 molar equivalents, 0.01 to 1.0 molar equivalents, 0.01 to 0.6 molar equivalents, 0.05 to 2.0 molar equivalents, 0.05 to 1.0 molar equivalents, 0.05 to 0.6 molar equivalents, 0.10 to 2.0 molar equivalents, 0.10 to 1.0 molar equivalents, or 0.10 to 0.6 molar equivalents. By keeping the amount of reducing agent below the above upper limit, it is possible to suppress an excessively high polymerization rate, prevent the polymer from becoming low molecular weight and the resulting liberation from the polymerization (A), and thus make it easier to obtain a polymerization product as designed.

[0100] When using transition metal salts as reducing agents, chelating agents can be used in combination to enhance their reactivity. Chelating agents can include compounds containing two or more electron-donating atoms that can form coordinate bonds with the target transition metal atom. 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.

[0101] The amount of chelating agent used is preferably 0.5 molar equivalent or more, more preferably 1.0 molar equivalent or more, relative to the transition metal salt reducing agent, from the viewpoint of controlling polymerization reactivity. On the other hand, it is preferably 5.0 molar equivalent or less, and more preferably 2.5 molar equivalent or less. The above upper and lower limits can be arbitrarily combined. For example, it may be 0.5 molar equivalent or more and 5.0 molar equivalent or less, 0.5 molar equivalent or more and 2.5 molar equivalent or less, 1.0 molar equivalent or more and 5.0 molar equivalent or less, or 1.0 molar equivalent or more and 2.5 molar equivalent or less.

[0102] In step 2, if necessary, an aqueous medium may be added to the polyorganosiloxane (A1) latex. Examples of aqueous mediums include water and mixed media of water and an organic solvent. The organic solvent in the mixed medium can be any solvent that is miscible with water, such as methanol and ethanol.

[0103] In step 2, an emulsifier may be added to the polyorganosiloxane (A1) latex as needed. The emulsifier is not particularly limited, and the same emulsifier used in the production of polyorganosiloxane (A1) described above can be used. Among these, anionic or nonionic emulsifiers are preferred. Alternatively, polymerization may be carried out using only the emulsifier contained in the polyorganosiloxane (A1) latex without adding an emulsifier in step 2.

[0104] 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. Among these, n-dodecyl mercaptan, t-dodecyl mercaptan, n-octyl mercaptan, and α-methylstyrene dimer are more preferred, n-dodecyl mercaptan, t-dodecyl mercaptan, and n-octyl mercaptan are even more preferred, t-dodecyl mercaptan and n-octyl mercaptan are particularly preferred, and n-octyl mercaptan is the most preferred. These chain transfer agents may be used individually or in combination of two or more.

[0105] The amount of chain transfer agent used is preferably 1.0 part by mass or less per 100 parts by mass of vinyl monomer component (a2), and may be 0 parts by mass. If the amount of chain transfer agent used is below the above upper limit, the decrease in the THF insoluble content ratio of composition (X) is suppressed, that is, the ratio of polymer (C) in composition (X) becomes a sufficient value, and the impact strength of the molded article is further improved.

[0106] <<Step 3>> The latex of the polyorganosiloxane (A1) to which the vinyl monomer component (a2) and radical polymerization initiator were added in Step 2 is heated to a temperature at least 10°C lower than the 10-hour half-life temperature of the radical polymerization initiator to initiate polymerization of the vinyl monomer component (a2).

[0107] By setting the polymerization initiation temperature of the vinyl monomer component (a2) (hereinafter referred to as polymerization temperature (A)) to a temperature at least 10°C lower than the 10-hour half-life temperature of the radical polymerization initiator, the polymerization rate can be suppressed. This prevents the polymer from becoming low molecular weight and the resulting liberation from polymer (A), making it easier to obtain a polymer as designed. As a result, a composition (X) containing polymer (C) that can improve the impact strength of the resulting molded article can be obtained. The polymerization temperature (A) is preferably at least 15°C lower than the 10-hour half-life temperature of the radical polymerization initiator, and more preferably at least 20°C lower. The polymerization time varies depending on the polymerization temperature (A), but is, for example, 0.1 to 30 hours.

[0108] The 10-hour half-life temperature is the temperature at which 50 mol% of the radical polymerization initiator used thermally decomposes in 10 hours. For example, the 10-hour half-life temperature T of the radical polymerization initiator can be calculated by substituting the conversion rate X = 50 [%], time t = 36000 [s] (= 10 hours), gas constant R = 8.314 [J / (mol·K)], frequency factor A, and activation energy E into the following equations (2) and (3). Literature values ​​may also be used as the 10-hour half-life temperature.

[0109] X = 100 × exp(-kdt) ... (2) kd = A × exp(-E / RT) ... (3) (In equation (2), "X [%]" is the conversion rate, "kd [1 / S]" is the reaction rate, and "t [s]" is time.) (In equation (3), "A [1 / S]" is the frequency factor, "E [J / mol]" is the activation energy, "R [J / (mol·K)]" is the gas constant, and "T [K]" is the temperature.) For example, the 10-hour half-life temperature of potassium persulfate is 67°C, and the 10-hour half-life temperature of t-butyl hydroperoxide (trade name Perbutyl H69, manufactured by NOF Corporation) is 167°C.

[0110] <Second Vinyl Polymer (B) Portion> The polymer (B) portion is a polymer obtained by polymerizing vinyl monomer component (b), and consists of units based on vinyl monomers. The vinyl monomer component (b) constituting the polymer (B) portion consists of one or more types of vinyl monomers. In this invention, the second vinyl polymer (B) portion is also simply referred to as "second vinyl polymer (B)" or "polymer (B)".

[0111] (Vinyl monomer component (b)) The vinyl monomer constituting vinyl monomer component (b) is not particularly limited, but examples include various vinyl monomers such as (meth)acrylate monomers (hereinafter also referred to as "monomer (b-1)"), aromatic vinyl monomers (hereinafter also referred to as "monomer (b-2)"), vinyl cyanide monomers (hereinafter also referred to as "monomer (b-3)"), and polyfunctional monomers (hereinafter also referred to as "monomer (b-4)"). Vinyl monomer component (b) preferably contains (meth)acrylate monomers and aromatic vinyl monomers.

[0112] Examples of monomer (b-1) include monomer (a2-1) as previously exemplified in the description of vinyl polymer (A2). Monomer (b-1) can be used alone or in combination of two or more types.

[0113] Examples of monomer (b-2) include aromatic vinyl monomers from among the monomers (a2-2) previously exemplified in the description of vinyl polymer (A2). Monomer (b-2) can be used individually or in combination of two or more types.

[0114] Examples of monomer (b-3) include the vinyl cyanide monomer, which is one of the monomers (a2-2) previously exemplified in the description of vinyl polymer (A2). Monomer (b-3) can be used individually or in combination of two or more types.

[0115] Examples of monomer (b-4) include monomer (a2-3) as previously exemplified in the description of vinyl polymer (A2). Monomer (b-4) can be used individually or in combination of two or more types.

[0116] The vinyl monomer component (b) preferably contains monomer (b-1) in terms of superior dispersibility of composition (X) in thermoplastic resin (E) and weather resistance of the molded article. When vinyl monomer component (b) contains monomer (b-1), the ratio of monomer (b-1) to the total mass of vinyl monomer component (b) is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more, while it may be 95% by mass or less, 90% by mass or less, or 85% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, it may be 10% by mass or more and 95% by mass or less, 10% by mass or more and 90% by mass or less, 10% by mass or more and 85% by mass or less, 15% by mass or more and 95% by mass or less, 15% by mass or more and 90% by mass or less, 15% by mass or more and 85% by mass or less, 20% by mass or more and 95% by mass or less, 20% by mass or more and 90% by mass or less, and 20% by mass or more and 85% by mass or less.

[0117] Among the monomers (b-1), vinyl monomer component (b) more preferably contains methyl methacrylate because it exhibits particularly excellent dispersibility of composition (X) in thermoplastic resin (E) and weather resistance of the molded article. When vinyl monomer component (b) contains methyl methacrylate, the ratio of methyl methacrylate to the total mass of vinyl monomer component (b) is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more. On the other hand, it may be 95% by mass or less, 90% by mass or less, or 85% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, it may be 10% by mass or more and 95% by mass or less, 10% by mass or more and 90% by mass or less, 10% by mass or more and 85% by mass or less, 15% by mass or more and 95% by mass or less, 15% by mass or more and 90% by mass or less, 15% by mass or more and 85% by mass or less, 20% by mass or more and 95% by mass or less, 20% by mass or more and 90% by mass or less, and 20% by mass or more and 85% by mass or less.

[0118] The vinyl monomer component (b) preferably contains monomer (b-2) in terms of superior dispersibility of composition (X) in thermoplastic resin (E). When vinyl monomer component (b) contains monomer (b-2), the ratio of monomer (b-2) to the total mass of vinyl monomer component (b) is preferably 5% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, while more preferably 90% by mass or less, even more preferably 80% by mass or less, and even more preferably 70% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, it may be 5% by mass or more and 90% by mass or less, 5% by mass or more and 80% by mass or less, 5% by mass or more and 70% by mass or less, 20% by mass or more and 90% by mass or less, 20% by mass or more and 80% by mass or less, 20% by mass or more and 70% by mass or less, 30% by mass or more and 90% by mass or less, 30% by mass or more and 80% by mass or less, and 30% by mass or more and 70% by mass or less. If the ratio of monomer (b-2) is equal to or greater than the lower limit, the dispersibility of composition (X) in thermoplastic resin (E) is better. If the ratio of monomer (b-2) is equal to or less than the upper limit, the amount of constituent units derived from aromatic vinyl monomers contained in the THF-soluble components of composition (X) can be easily kept within the above range, and the colored appearance of the molded article is better.

[0119] Among the monomers (b-2), vinyl monomer component (b) more preferably contains styrene because it exhibits particularly excellent dispersibility of composition (X) in thermoplastic resin (E). When vinyl monomer component (b) contains styrene, the ratio of styrene to the total mass of vinyl monomer component (b) is preferably 5% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, while on the other hand, it is more preferably 90% by mass or less, even more preferably 80% by mass or less, and even more preferably 70% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, the amount may be 5% by mass or more and 90% by mass or less, 5% by mass or more and 80% by mass or less, 5% by mass or more and 70% by mass or less, 20% by mass or more and 90% by mass or less, 20% by mass or more and 80% by mass or less, 20% by mass or more and 70% by mass or less, 30% by mass or more and 90% by mass or less, 30% by mass or more and 80% by mass or less, or 30% by mass or more and 70% by mass or less. If the ratio of styrene is above the lower limit, the dispersibility of composition (X) in thermoplastic resin (E) is better. If the ratio of styrene is below the upper limit, the amount of constituent units derived from aromatic vinyl monomers contained in the THF-soluble components of composition (X) can be easily kept within the above range, and the colored appearance of the molded article is better.

[0120] The vinyl monomer component (b) preferably contains monomer (b-1) and monomer (b-2) in terms of having superior weather resistance in the molded article. When the vinyl monomer component (b) contains monomer (b-1) and monomer (b-2), the ratio of the total amount of monomer (b-1) and monomer (b-2) to the total mass of vinyl monomer component (b) is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 80% by mass or more. On the other hand, it may be 100% by mass or less, 95% by mass or less, or 90% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, it may be 50% by mass or more and 100% by mass or less, 50% by mass or more and 95% by mass or less, 50% by mass or more and 90% by mass or less, 60% by mass or more and 100% by mass or less, 60% by mass or more and 95% by mass or less, 60% by mass or more and 90% by mass or less, 80% by mass or more and 100% by mass or less, 80% by mass or more and 95% by mass or less, and 80% by mass or more and 90% by mass or less.

[0121] When vinyl monomer component (b) contains monomer (b-1) and monomer (b-2), monomer (b-1) is preferably methyl methacrylate. When vinyl monomer component (b) contains monomer (b-1) and monomer (b-2), monomer (b-2) is preferably styrene. When vinyl monomer component (b) contains monomer (b-1) and monomer (b-2), monomer (b-1) is preferably methyl methacrylate and monomer (b-2) is preferably styrene.

[0122] When the vinyl monomer component (b) contains monomer (b-1) and monomer (b-2), the ratio of the total of methyl methacrylate and monomer (b-2), or the total of monomer (b-1) and styrene, or the total of methyl methacrylate and styrene, to the total mass of vinyl monomer component (b) is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 80% by mass or more. On the other hand, it may be 100% by mass or less, 95% by mass or less, or 90% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, it may be 50% by mass or more and 100% by mass or less, 50% by mass or more and 95% by mass or less, 50% by mass or more and 90% by mass or less, 60% by mass or more and 100% by mass or less, 60% by mass or more and 95% by mass or less, 60% by mass or more and 90% by mass or less, 80% by mass or more and 100% by mass or less, 80% by mass or more and 95% by mass or less, and 80% by mass or more and 90% by mass or less.

[0123] Furthermore, the vinyl monomer component (b) is preferably composed of monomer (b-3) in terms of its excellent dispersibility in the thermoplastic resin (E) of composition (X). When the vinyl monomer component (b) contains monomer (b-3), the ratio of monomer (b-3) to the total mass of vinyl monomer component (b) may be 3% by mass or more, 5% by mass or more, 10% by mass or more, 12% by mass or more, 14% by mass or more, 16% by mass or more, on the other hand, it may be 50% by mass or less, 40% by mass or less, 35% by mass or less, 30% by mass or less, 25% by mass or less, or 20% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, it may be 3 to 50% by mass, 3 to 40% by mass, 3 to 35% by mass, 3 to 30% by mass, 3 to 25% by mass, 3 to 20% by mass, 5 to 50% by mass, 5 to 40% by mass, 5 to 35% by mass, 5 to 30% by mass, 5 to 25% by mass, 5 to 20% by mass, 10 to 50% by mass, 10 to 40% by mass, 10 to 35% by mass, 10 to 30% by mass, 10 to 25% by mass, 10 to 20% by mass, 12 to 5 It may be 0% by mass, 12 to 40% by mass, 12 to 35% by mass, 12 to 30% by mass, 12 to 25% by mass, 12 to 20% by mass, 14 to 50% by mass, 14 to 40% by mass, 14 to 35% by mass, 14 to 30% by mass, 14 to 25% by mass, 14 to 20% by mass, 16 to 50% by mass, 16 to 40% by mass, 16 to 35% by mass, 16 to 30% by mass, 16 to 25% by mass, and 16 to 20% by mass.

[0124] Among the monomers (b-3), the vinyl monomer component (b) more preferably contains at least one selected from acrylonitrile and methacrylonitrile, and even more preferably contains acrylonitrile, as this results in a better colored appearance of the molded product. If the vinyl monomer component (b) contains acrylonitrile or methacrylonitrile, the ratio of the total amount of acrylonitrile and methacrylonitrile to the total mass of the vinyl monomer component (b) may be 0.1% by mass or more, 1% by mass or more, 2% by mass or more, 3% by mass or more, 4% by mass or more, 5% by mass or more, 10% by mass or more, 11% by mass or more, 12% by mass or more, 13% by mass or more, 14% by mass or more, 15% by mass or more, 16% by mass or more, 17% by mass or more, while on the other hand, it may be 50% by mass or less, 40% by mass or less, 35% by mass or less, 30% by mass or less, 25% by mass or less, or 20% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, it may be 0.1 to 50 mass%, 0.1 to 40 mass%, 0.1 to 35 mass%, 0.1 to 30 mass%, 0.1 to 25 mass%, 0.1 to 20 mass%, 1 to 50 mass%, 1 to 40 mass%, 1 to 35 mass%, 1 to 30 mass%, 1 to 25 mass%, 1 to 20 mass%, 2 to 50 mass%, 2 to 40 mass%, 2 to 35 mass%, 2 to 30 mass%, 2 to 25 mass It may be %, may be 2 to 20 mass%, may be 3 to 50 mass%, may be 3 to 40 mass%, may be 3 to 35 mass%, may be 3 to 30 mass%, may be 3 to 25 mass%, may be 3 to 20 mass%, may be 4 to 50 mass%, may be 4 to 40 mass%, may be 4 to 35 mass%, may be 4 to 30 mass%, may be 4 to 25 mass%, may be 4 to 20 mass%, may be 5 to 50 mass%, may be 5 to 40 mass%, may be 5 to 35 mass%, may be 5 to 30 mass,It may be 5 to 25% by mass, 5 to 20% by mass, 10 to 50% by mass, 10 to 40% by mass, 10 to 35% by mass, 10 to 30% by mass, 10 to 25% by mass, 10 to 20% by mass, 11 to 50% by mass, 11 to 40% by mass, 11 to 35% by mass, 11 to 30% by mass, and 11 to 25% by mass. It may be present, may be 11-20% by mass, may be 12-50% by mass, may be 12-40% by mass, may be 12-35% by mass, may be 12-30% by mass, may be 12-25% by mass, may be 12-20% by mass, may be 13-50% by mass, may be 13-40% by mass, may be 13-35% by mass, may be 13-30% by mass, may be 13-25% by mass, 1 It may be 3 to 20% by mass, 14 to 50% by mass, 14 to 40% by mass, 14 to 35% by mass, 14 to 30% by mass, 14 to 25% by mass, 14 to 20% by mass, 15 to 50% by mass, 15 to 40% by mass, 15 to 35% by mass, 15 to 30% by mass, 15 to 25% by mass, 15 to 20% by mass It may be 16-50% by mass, 16-40% by mass, 16-35% by mass, 16-30% by mass, 16-25% by mass, 16-20% by mass, 17-50% by mass, 17-40% by mass, 17-35% by mass, 17-30% by mass, 17-25% by mass, or 17-20% by mass.

[0125] Furthermore, the vinyl monomer component (b) preferably contains monomer (b-4) in terms of its excellent dispersibility in the thermoplastic resin (E) of composition (X). When the vinyl monomer component (b) contains monomer (b-4), the ratio of monomer (b-4) to the total mass of vinyl monomer component (b) may be 0% by mass or more, 0.1% by mass or more, 0.3% by mass or more, 0.5% by mass or more, 1.0% by mass or more, on the other hand, it may be 10% by mass or less, 7.5% by mass or less, or 5.0% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, it may be 0 to 10% by mass, 0 to 7.5% by mass, 0 to 5.0% by mass, 0.1 to 10% by mass, 0.1 to 7.5% by mass, 0.1 to 5.0% by mass, 0.3 to 10% by mass, 0.3 to 7.5% by mass, 0.3 to 5.0% by mass, 0.5 to 10% by mass, 0.5 to 7.5% by mass, 0.5 to 5.0% by mass, 1.0 to 10% by mass, 1.0 to 7.5% by mass, and 1.0 to 5.0% by mass.

[0126] The vinyl monomer component (b) is more preferably selected from the group consisting of allyl methacrylate, triallyl cyanurate, and triallyl isocyanurate, and more preferably contains allyl methacrylate, since this results in a better colored appearance of the molded article. When the vinyl monomer component (b) contains allyl methacrylate, triallyl cyanurate, or triallyl isocyanurate, the ratio of the total amount of allyl methacrylate, triallyl cyanurate, and triallyl isocyanurate to the total mass of vinyl monomer component (b) may be 0% by mass or more, 0.1% by mass or more, 0.3% by mass or more, 0.5% by mass or more, 1.0% by mass or more, on the other hand, it may be 10% by mass or less, 7.5% by mass or less, or 5.0% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, it may be 0 to 10% by mass, 0 to 7.5% by mass, 0 to 5.0% by mass, 0.1 to 10% by mass, 0.1 to 7.5% by mass, 0.1 to 5.0% by mass, 0.3 to 10% by mass, 0.3 to 7.5% by mass, 0.3 to 5.0% by mass, 0.5 to 10% by mass, 0.5 to 7.5% by mass, 0.5 to 5.0% by mass, 1.0 to 10% by mass, 1.0 to 7.5% by mass, and 1.0 to 5.0% by mass.

[0127] (Glass transition temperature) The glass transition temperature (hereinafter also referred to as "Tg") of the polymer (B) portion 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 polymer (B) portion is above the lower limit, the powder properties (powder fluidity and particle size) of composition (X) will be good. The above upper and lower limits can be combined arbitrarily. For example, it may be 70 to 105°C, 80 to 105°C, or 90 to 105°C. The Tg of the polymer (B) portion can be adjusted by the type and ratio of vinyl monomers constituting the vinyl monomer component (b).

[0128] The Tg of 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 the value described in, for example, "Polymer Handbook" (Wiley Interest, Inc. / 1999). The Tg of vinyl monomer homopolymers not described in this document can be calculated using Bicerano's method, "Prediction of Polymer Properties" (Marcel Decker, Inc. / 2002).

[0129] "Other components" Other components are components of composition (X) other than polymer (C). Examples of other components include unreacted monomers used in the production of polymer (C), polymers formed by the polymerization of unreacted monomers (other polymers that do not fall under polymer (C)), polymerization initiators, chain transfer agents, oxidation-reduction aids, and emulsifiers used in the production of polymer (C). Other components may include, for example, aromatic vinyl monomers and polymer (S).

[0130] If composition (X) contains other components, the ratio of the other components to the total mass of composition (X) is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, and particularly preferably 7% by mass or less. On the other hand, it may be 0% by mass, greater than 0% by mass, or 1% by mass or more. The above upper and lower limits can be combined arbitrarily. For example, it may be 0 to 20% by mass, 0 to 15% by mass, 0 to 10% by mass, 0 to 7% by mass, greater than 0% by mass to 20% by mass, greater than 0% by mass to 15% by mass, greater than 0% by mass to 10% by mass, greater than 0% by mass to 7% by mass, 1 to 20% by mass, 1 to 15% by mass, 1 to 10% by mass, and 1 to 7% by mass.

[0131] "Method for producing composition (X)" Composition (X) is obtained by producing polymer (C). Polymer (C) can be produced, for example, by polymerizing vinyl monomer component (b) (graft polymerization) in the presence of polymer (A). This yields composition (X) which contains polymer (C), a polymer in which part or all of polymer (B) is grafted onto polymer (A). Note that among the monomers contained in vinyl monomer component (b), unreacted monomers that were not used in graft polymerization, and other polymers that do not correspond to polymer (C) may remain in the reaction system. In that case, polymer (C) is obtained in the form of a mixture of these unreacted monomers and other polymers that do not correspond to polymer (C). The unreacted monomers and other polymers that do not correspond to polymer (C) correspond to other components that may be contained in composition (X), and a mixture containing polymer (C) and the unreacted monomers and other polymers that do not correspond to polymer (C) can be used as composition (X).

[0132] A preferred method for producing composition (X) is to add vinyl monomer component (b) to the latex of polymer (A) and polymerize vinyl monomer component (b) in the latex of polymer (A). The latex of polymer (A) is preferably produced by polymerizing vinyl monomer component (a2) in the presence of a latex containing polyorganosiloxane (A1), as described above. If unreacted monomers that were not used in the polymerization of the organosiloxane mixture or the polymerization of vinyl monomer component (a2), or other polymers that do not correspond to polymer (C), remain in the latex of polymer (A), these unreacted monomers and their polymers may also be included in composition (X) as other components.

[0133] The temperature used for polymerizing the vinyl monomer component (b) is not particularly limited, and conventional conditions can be applied, such as 45 to 95°C and a polymerization time of 0.1 to 10 hours.

[0134] 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 continuously, or it may be added dropwise in multiple steps with holding periods in between during which vinyl monomer component (b) is not added. When vinyl monomer component (b) consists of multiple types of vinyl monomers, the method for adding the entire amount of vinyl monomer component (b) dropwise continuously is not particularly limited and includes methods such as continuously adding a mixture of the same composition, or adding while continuously changing the composition, as in power feed polymerization. When vinyl monomer component (b) consists of multiple types of vinyl monomers, methods for adding it dropwise in multiple steps with holding periods in between include adding a mixture of the same composition in multiple steps, or adding each component individually and / or a mixture of different compositions in multiple steps.

[0135] When the vinyl monomer component (b) contains monomers (b-1), (b-2), and (b-3), it is preferable to polymerize monomer (b-1), and then monomers (b-2) and (b-3). Polymerization in this manner results in good properties (fluidity and particle size when composition (X) is a powder) of the composition (X) containing the polymer (C) obtained by a powder recovery step after polymerization.

[0136] The vinyl monomer component (b) can easily 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). To improve the efficiency of this grafting, monomer (b-4), for example, can be polymerized beforehand before polymerization of monomers (b-1), (b-2), and (b-3).

[0137] 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.

[0138] 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 all monomers used in the production of polymer (C). The above upper and lower limits can be arbitrarily combined. For example, it may be 0.05 parts by mass or more and 10 parts by mass or less, 0.05 parts by mass or more and 5 parts by mass or less, 0.1 parts by mass or more and 10 parts by mass or less, or 0.1 parts by mass or more and 5 parts by mass or less. The total amount of emulsifier makes it possible to adjust the latex particle size of composition (X) containing polymer (C) to a desired value. 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 composition (X) containing 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 composition (X) containing polymer (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 composition (X) and thermoplastic resin (E) can be suppressed.

[0139] When polymerizing the vinyl monomer component (b), a polymerization initiator may be used for purposes such as adjusting the THF-soluble content. Examples of polymerization initiators include those exemplified earlier in the description of the production of polymer (A). A single polymerization initiator may be used, or two or more may be used in combination.

[0140] The amount of polymerization initiator used is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, and even more preferably 0.4 parts by mass or more, per 100 parts by mass of vinyl monomer component (b). On the other hand, it may be 2.0 parts by mass or less, 1.5 parts by mass or less, or 1.0 part by mass or less. The above upper and lower limits can be combined arbitrarily. For example, it may be 0.1 parts by mass or more and 2.0 parts by mass or less, 0.1 parts by mass or more and 1.5 parts by mass or less, 0.1 parts by mass or more and 1.0 part by mass or less, 0.2 parts by mass or more and 2.0 parts by mass or less, 0.2 parts by mass or more and 1.5 parts by mass or less, 0.2 parts by mass or more and 1.0 part by mass or less, 0.4 parts by mass or more and 2.0 parts by mass or less, 0.4 parts by mass or more and 1.5 parts by mass or less, or 0.4 parts by mass or more and 1.0 part by mass or less. If the amount of polymerization initiator used is equal to or greater than the lower limit, the amount of constituent units derived from aromatic vinyl monomers contained in the THF-soluble components of composition (X) can be easily kept within the above-mentioned range, resulting in a superior colored appearance of the molded article.

[0141] When a peroxide is used as a radical polymerization initiator in the polymerization of the vinyl monomer component (b), a reducing agent can be used in combination to promote the decomposition of the peroxide. Examples of reducing agents include those previously exemplified in the description of the production of polymer (A). Among these, sodium formaldehyde sulfoxylate, L(+)-tartaric acid, sodium disulfite, sodium isoascorbate and L-ascorbic acid, and ferrous sulfate are preferred because they are readily available industrially and the molded article exhibits superior heat resistance, discoloration, and surface appearance. Of these, sodium formaldehyde sulfoxylate, sodium isoascorbate, L-ascorbic acid, and ferrous sulfate are more preferred, sodium formaldehyde sulfoxylate, L-ascorbic acid, and ferrous sulfate are even more preferred, sodium formaldehyde sulfoxylate and ferrous sulfate are particularly preferred, and ferrous sulfate is the most preferred.

[0142] 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, and even more preferably 0.6 molar equivalents or less. By keeping the amount of reducing agent below the above upper limit, it is possible to suppress an excessively high polymerization rate, thereby suppressing the compositional differences of polymer (B) and the resulting deterioration of the physical properties of the molded article containing polymer (C). Furthermore, by using a reducing agent, it is possible to suppress a significant decrease in the polymerization rate and the resulting prolonged polymerization time, thereby preventing difficulties in actual manufacturing.

[0143] When using transition metal salts as reducing agents, chelating agents can be used in combination to enhance their reactivity. Examples of chelating agents include those exemplified earlier in the description of the production of polymer (A). Among these, ethylenediaminetetraacetic acid and its metal salts are preferred due to their excellent polymerization stability.

[0144] From the standpoint of controlling polymerization reactivity, the amount of chelating agent used is preferably 0.5 molar equivalent or more, more preferably 1.0 molar equivalent or more, and on the other hand, preferably 5.0 molar equivalent or less, relative to the transition metal salt reducing agent.

[0145] When polymerizing the vinyl monomer component (b), a chain transfer agent may be used for purposes such as adjusting the THF-soluble content and the weight-average molecular weight of the THF-soluble content and composition (X). Examples of chain transfer agents include those exemplified earlier in the description of the production of polymer (A). One type of chain transfer agent may be used alone, or two or more types may be used in combination.

[0146] The amount of chain transfer agent used may be 2.0 parts by mass or less, 1.0 part by mass or less, 0.5 parts by mass or less, 0.1 parts by mass or less, 0.05 parts by mass or less, or 0 parts by mass, per 100 parts by mass of vinyl monomer component (b). If the amount of chain transfer agent used is below the above upper limit, the decrease in the ratio of THF-insoluble components in composition (X) is suppressed, that is, the ratio of polymer (C) in composition (X) becomes a sufficient value, and the impact strength of the molded article is further improved. In addition, the amount of constituent units derived from aromatic vinyl monomers contained in the THF-soluble components in composition (X) can be easily kept within the above range, and the colored appearance of the molded article is further improved.

[0147] After polymerizing the vinyl monomer component (b), composition (X) may be recovered from the latex of composition (X) containing the obtained polymer (C). When recovering composition (X), 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 and initiators 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 composition (X) is added to the thermoplastic resin (E).

[0148] The spray drying method involves spraying the latex of composition (X) into a dryer in the form of fine droplets and drying it by applying a heating gas for drying. 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 capacities suitable for laboratory use to large capacities suitable for 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 of composition (X) before spray drying.

[0149] The coagulation method is a method for separating, recovering, and drying composition (X) by coagulating the latex of composition (X). First, the latex of composition (X) is placed in hot water in which a coagulant has been dissolved, and composition (X) is separated by salting out and coagulation. Next, the separated wet composition (X) is dehydrated or otherwise processed to recover the composition (X) with reduced moisture content. The recovered composition (X) is dried using a press dewatering machine or a hot air dryer.

[0150] 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.

[0151] The coagulant is usually used as an aqueous solution. From the viewpoint of stably solidifying and recovering composition (X), the concentration of the aqueous coagulant solution is 0.1% by mass or more, preferably 1% by mass or more. Furthermore, from the viewpoint of reducing the amount of coagulant remaining in the recovered composition (X) and preventing deterioration of the molded appearance of the molded article, the concentration of the aqueous coagulant solution is 20% by mass or less, preferably 15% by mass or less. The above upper and lower limits can be arbitrarily combined. For example, it may be 0.1% by mass or more and 20% by mass or less, 0.1% by mass or more and 15% by mass or less, 1% by mass or more and 20% by mass or less, or 1% by mass or more and 15% by mass or less. The amount of aqueous coagulant 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 in composition (X).

[0152] The method for contacting the latex of composition (X) with the coagulant aqueous solution is not particularly limited, but the following methods are commonly used: (1) Continuously adding the latex to the coagulant aqueous solution while stirring it and holding it there for a certain period of time. (2) Continuously injecting the coagulant aqueous solution and the latex into a container equipped with a stirrer at a constant ratio, bringing them into contact, and continuously withdrawing the mixture containing the coagulated polymer and water from the container. The temperature when contacting the latex with the coagulant aqueous solution is not particularly limited, but it is preferably 30°C or higher and 100°C or lower. The contact time is not particularly limited.

[0153] The coagulated composition (X) is washed with water in an amount of 1 to 100 times its mass and filtered. The filtered, wet composition (X) 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 resulting composition (X). Alternatively, the composition (X) discharged from the press dewatering machine or extruder may not be recovered, but sent directly to an extruder or molding machine that manufactures resin compositions, where it can be mixed with a thermoplastic resin (E) to obtain a molded product.

[0154] The composition (X) obtained in this way contains polymer (C). However, as described above, if unreacted monomers not used in polymerization or other polymers that do not correspond to polymer (C) remain in the reaction system, the composition (X) will be obtained containing these unreacted monomers and other polymers that do not correspond to polymer (C) as other components. If necessary, the composition (X) may be purified to remove the other components to obtain a composition (X) consisting only of polymer (C), or the composition (X) containing the other components may be mixed with the thermoplastic resin (E) described later.

[0155] [Resin Composition] A resin composition according to one aspect of the present invention (hereinafter also referred to as "resin composition (Z)") comprises composition (X) of the present invention and thermoplastic resin (E). Resin composition (Z) may further contain components other than composition (X) and thermoplastic resin (E) (hereinafter also referred to as "optional components") as necessary, as long as they do not impair the effects of the present invention.

[0156] <Thermoplastic Resin (E)> The thermoplastic resin (E) is not particularly limited and includes, for example, acrylic resin, engineering plastics (aromatic polycarbonate, etc.), styrene resin, polyester resin, olefin resin (polyethylene resin, polypropylene resin, etc.), thermoplastic elastomer, biodegradable resin, halogen resin (vinyl chloride resin, etc.). Among these, acrylic resin, polypropylene resin, and polyethylene resin corresponding to the thermoplastic resin (E1) described above are preferred, and acrylic resin is more preferred. These thermoplastic resins (E) can be used individually or in combination of two or more.

[0157] Examples of acrylic resins include polymers containing constituent units derived from (meth)acrylate monomers. Specifically, examples include homopolymers of methyl methacrylate (polymethyl methacrylate); and copolymers of methyl methacrylate and vinyl monomers copolymerizable with methyl methacrylate. Examples of (meth)acrylate monomers include monomer (a2-1) which was previously exemplified in the description of vinyl polymer (A2). Examples of vinyl monomers copolymerizable with methyl methacrylate 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. Among these, methyl acrylate, n-butyl acrylate, n-butyl methacrylate, and styrene are more preferred, methyl acrylate, n-butyl acrylate, and styrene are even more preferred, methyl acrylate and styrene are particularly preferred, and methyl acrylate is the most preferred. These acrylic resins can be used individually or in combination of two or more. Polymethyl methacrylate is more preferred because it is industrially readily available and offers a superior balance between the impact strength and colorability of the molded article.

[0158] <Optional Components> Optional components include various additives such as flame retardants (e.g., 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., phenol-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.), and colorants. These optional components can be used individually or in combination of two or more.

[0159] Examples of colorants include pigments such as inorganic pigments, organic pigments, and special pigments; and dyes. Examples of inorganic pigments include 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. Examples of 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 colorants 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 types.

[0160] <Ratio> The ratio of composition (X) to the total mass of resin composition (Z) is preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 2% by mass or more, while preferably 60% by mass or less, and more preferably 50% by mass or less. The above upper and lower limits can be arbitrarily combined. For example, it may be 0.5% by mass or more and 60% by mass or less, 0.5% by mass or more and 50% by mass or less, 1% by mass or more and 60% by mass or less, 1% by mass or more and 50% by mass or less, 2% by mass or more and 60% by mass or less, and 2% by mass or more and 50% by mass or less. If the ratio of composition (X) 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 (Z) can be suppressed.

[0161] The ratio of thermoplastic resin (E) to the total mass of the resin composition (Z) 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. The above upper and lower limits can be arbitrarily combined. For example, it may be 40% by mass or more and 99.5% by mass or less, 40% by mass or more and 99% by mass or less, 40% by mass or more and 98% by mass or less, 50% by mass or more and 99.5% by mass or less, 50% by mass or more and 99% by mass or less, and 50% by mass or more and 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 (Z) can be suppressed, and if it is below the upper limit, the impact strength of the resulting molded article is better.

[0162] <Method for producing resin composition (Z)> Resin composition (Z) can be produced by mixing composition (X), thermoplastic resin (E), and optional components as needed. Known blending methods are available for mixing each material, and are not particularly limited. 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 resin composition (Z), composition (X), pelletized thermoplastic resin (E), and optional components as needed can be mixed using an extruder, extruded into a strand, and cut into pellets with a rotary cutter or the like. By this method, pelletized resin composition (Z) can be obtained.

[0163] [Molded Article] A molded article according to one aspect of the present invention (hereinafter also referred to as "the molded article") contains the resin composition (Z) of the present invention. Therefore, the molded article contains composition (X). The molded article is a molded article containing the resin composition (Z), and the molded article contains a thermoplastic resin (E) in addition to composition (X), and may further contain one or more optional components as needed.

[0164] This molded article can be manufactured, for example, by molding a resin composition (Z). Examples of molding methods include those commonly used for molding thermoplastic resin compositions, such as injection molding, extrusion molding, blow molding, and calendering.

[0165] 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.

[0166] The present invention will be described in more detail below with reference to manufacturing examples and embodiments, but the present invention is not limited to the following description. Note that "parts" means "parts by mass" and "%" means "percent by mass".

[0167] [Measurement and Evaluation] <Measurement of Solid Content> Latex of polyorganosiloxane (A1) with mass w1, or latex of composition (X), was dried in a hot air dryer at 180°C for 30 minutes. The mass w2 of the residue after drying was measured, and the solid content [%] was calculated using the following formula (4). Solid content [%] = w2 / w1 × 100 ... (4)

[0168] <Measurement of Particle Size> The latex of polyorganosiloxane (A1) or the latex of composition (X) was diluted to a concentration of approximately 3% with deionized water. The resulting diluted solution was used as a sample, and the particle size distribution was measured on a number basis or by mass basis using a capillary particle size analyzer (product name "CHDF2000" manufactured by MATEC, Inc., USA), and the median diameter was taken as the number-average particle size or mass-average particle size. As standard particle size materials, 12 types of monodisperse polystyrene with known particle sizes, manufactured by DUKE, Inc., USA, with particle sizes ranging from 40 to 800 nm were used. The measurement of the particle size distribution is as follows. - Cartridge: Dedicated capillary cartridge for particle separation (product name: C-202), - Carrier solution: Dedicated carrier solution (product name: 2XGR500), - pH of carrier solution: Neutral, - Flow rate of carrier solution: 1.4 mL / min, - Pressure of carrier solution: Approximately 4,000 psi (2,600 kPa), - Measurement temperature: 35°C, - Sample volume used: 0.1 mL.

[0169] <Measurement of THF-insoluble components> The THF-insoluble components of composition (X) were measured according to the following method. (1-1): 0.5 g of the sample was added to 50 mL (44.5 g) of THF, left to stand at 25°C for 8 hours, and then stirred with a stirrer for 30 minutes to dissolve the THF-soluble components in THF, obtaining a mixture. (1-2): The mixture obtained in (1-1) was placed in a centrifuge tube whose mass was measured, and the liquid containing the THF-insoluble components and the THF-soluble components (supernatant) was centrifuged using a centrifuge (16000 rpm, 4 hours). (1-3): After separating the supernatant containing the THF-soluble components, fresh THF was added to the THF-insoluble components and stirred, and centrifugation was performed again in the same manner as in (1-2) to wash away the THF-insoluble components. (1-4): After repeating (1-3) twice, the supernatant was removed. The centrifuge tube containing the remaining THF-insoluble matter was immersed in a hot water bath (80°C, 8 hours) to volatilize the THF, and then vacuum-dried at 65°C for 6 hours to obtain a dried sample (THF-insoluble matter adhering to the centrifuge tube). (1-5): The mass of the obtained dried sample (THF-insoluble matter + centrifuge tube) was measured, and the THF-insoluble matter content ratio w was calculated using the following formula (1). ａｉｓ (%) was calculated. ａｉｓ = (w ｃ１ -w ａｓ ) / wt × 100 ... (1) (In formula (1), "wt" is the mass of the composition (X) used for measurement, and "w ａｓ " is the mass of the centrifuge tube, and "w ｃ１ This represents the mass of the THF-insoluble portion (including the centrifuge tube).

[0170] <Measurement of Weight-Average Molecular Weight of THF-Soluble Components> The weight-average molecular weight of THF-soluble components was measured by performing the following operations (2-1) to (2-3). (2-1): From the supernatant containing THF-soluble components separated in the previous section [Measurement of THF-Insoluble Components], THF was removed under reduced pressure using a rotary evaporator to obtain THF-soluble components. (2-2): The THF-soluble components obtained in (2-1) were dissolved again in THF to a sample concentration of 0.1-0.3% to obtain a THF solution of THF-soluble components. (2-3): Gel permeation chromatography (GPC) was performed on the THF solution of THF-soluble components obtained in (2-2), and the weight-average molecular weight (Mw) was determined from a calibration curve using standard polystyrene. The GPC measurement conditions are as follows. • Apparatus: Tosoh Corporation, product name "HLC8220", • Column: Tosoh Corporation, product name "TSKgel SuperMultiporeHZ-H" (inner diameter 4.6 mm x length 15 cm x 2, exclusion limit 4 x 10) ７ (Estimated)), - Eluent: THF, - Eluent flow rate: 0.35 mL / min, - Measurement temperature: 40°C, - Sample injection amount: 10 μL.

[0171] <Compositional analysis of THF-soluble components> The amount of constituent units derived from aromatic vinyl monomers contained in the THF-soluble components is: １ This was determined by performing 1H-NMR measurement. The THF soluble matter obtained in (2-1) of the previous section [Measurement of weight-average molecular weight of THF soluble matter] was mixed with dichloromethane-d to a concentration of 0.03 mg / 0.6 mL. ２ Dissolve in it and use as a measurement sample. １ H-NMR measurements were performed. １ The measurement conditions for H-NMR are as follows: • Apparatus: JEOL Ltd., product name "ECZ500R", • Probe: Royal φ5mm, • Temperature: Room temperature, • Nuclide: １ H. FID acquisition time: 3.4918 seconds, Waiting time: 7 seconds, Total number of calculations: 512.

[0172] １ ​The amount of constituent units derived from aromatic vinyl monomers was calculated by multiplying the molecular weight of the aromatic vinyl monomer by the molecular weight of the aromatic vinyl monomer, thereby determining the total weight of aromatic vinyl monomers and polymers (S) contained in the THF soluble matter. Next, the amount of constituent units derived from aromatic vinyl monomers was divided by the total weight of constituent units other than those derived from aromatic vinyl monomers (other constituent units) contained in the THF soluble matter, which were similarly measured and calculated. The ratio of THF soluble matter (100-w) was then calculated. ａｉｓ By multiplying by ), the amount of constituent units derived from aromatic vinyl monomers contained in 100% by mass of composition (X) was determined.

[0173] <Measurement of Charpy Impact Strength> A TYPE A notch, in accordance with ISO 179-1, was engraved on test specimen A (described later), and the Charpy impact strength was measured at 23°C and evaluated using the following index. A higher value indicates better impact resistance and is preferable. A: 6 kJ / m ２ More than B: 4kJ / m ２ Above, 6kJ / m ２ Less than C: 4 kJ / m ２ less than

[0174] <Measurement of Bending Modulus> The bending modulus was measured on specimen A (described later) using a tensile-compression testing machine (manufactured by Toyo Seiki Seisakusho Co., Ltd., product name "Strograph T") in accordance with JIS K 7171 at a measurement temperature of 23°C, and evaluated using the following index. A higher value indicates higher rigidity, which is preferable. A: 2100 MPa or higher B: 2000 MPa or higher, less than 2100 MPa C: Less than 2000 MPa

[0175] <Evaluation of Colored Appearance> As an indicator of the colored appearance of the molded product, the color difference (ΔE) was evaluated according to the following method. Using a spectrocolorimeter (manufactured by Nippon Denshoku Industries Ltd., product name "SD7000"), hue measurement was performed on test piece B described later using the SCE method, and L was determined in accordance with ISO 11664-4. ＊ a ＊ and b ＊The following indicators were used to determine and evaluate the results. In this example, the resin composition obtained by adding only the colorants OD-1 to OD-3 (described later) in the same proportions as in the examples or comparative examples shown in Table 3, without adding composition (X) to 100 parts by mass of acrylic resin (PMMA), was molded into a test piece (hereinafter referred to as "blank") measuring 100 mm in length, 50 mm in width, and 2 mm in thickness. The measurement results (L ＊ = 0.3, a ＊ = 0.2, b ＊ Using -0.3 as the baseline, the color difference ΔE was calculated using the following formula (5): ΔE = ((ΔL ＊ ) ２ + (Δa ＊ ) ２ + (Δb ＊ ) ２ ) ０．５ ... (5) Here, "ΔL ＊ " is the L between the blank and each test piece ＊ The difference, "Δa ＊ " is the a between the blank and each test piece ＊ The difference, "Δb" ＊ " is the difference between the blank and each test piece ＊ This shows the difference.

[0176] A lower ΔE value indicates a closer match between the blank and the color, resulting in superior color development and a better colored appearance (jet blackness), which is desirable. Generally, if the color difference ΔE is 1.2 or higher, most people can easily recognize the color difference when comparing them side by side. For convenience, the ΔE values ​​are broadly categorized into three types, but within the same index, a lower ΔE value is preferable. For example, ΔE = 1.3 (B) can be interpreted as being better than ΔE = 2.4 (B). A: Less than 1.2 B: 1.2 or higher, less than 2.5 C: 2.5 or higher

[0177] <Evaluation of the degree of yellowing due to high temperature> During injection molding, the degree of yellowing was evaluated under molding condition 2 described below, which was at a higher temperature than molding condition 1 and allowed to remain in place. To evaluate the degree of yellowing after injection molding under molding condition 2, a spectrocolorimeter (manufactured by Nippon Denshoku Industries Ltd., product name "SD7000") was used, as in the <Evaluation of colored appearance> above, and hue measurement was performed on a test piece B measuring 100 mm in length x 50 mm in width x 2 mm in thickness using the SCE method, and the result was determined in accordance with ISO 11664-4. ＊ We sought b. ＊ A higher value indicates a stronger yellow tint, therefore, in this evaluation, b ＊ A small value is preferable.

[0178] [Example 1] <Production of Polyorganosiloxane (A1-1)> 98 parts of a cyclic organosiloxane mixture (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "DMC", a mixture of cyclic organosiloxanes with 3 to 6 member rings) and 2 parts of 3-methacryloxypropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade 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, trade name "Neoperex G-15", on a solid content basis) in 300 parts of deionized water was added to the organosiloxane 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, trade name "Neoperex GS") in 90 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 (A1-1) latex. The solid content of the polyorganosiloxane (A1-1) latex was 20%. Furthermore, the number-average particle size (Dn) of this latex measured by a capillary particle size analyzer was 26 nm, the mass-average particle size (Dw) was 35 nm, and the Dw / Dn ratio was 1.35.

[0179] <Preparation of Composition (X-1)> 18 parts of the polyorganosiloxane (A1-1) latex obtained earlier (3.0 parts in polymer equivalent) were taken into a 5-liter separable flask, and 170 parts of deionized water were added and mixed. Next, 66.1 parts of n-butyl acrylate (nBA), 0.3 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. 0.08 parts of potassium persulfate (KPS), 0.0005 parts of ferrous sulfate heptahydrate, 0.0030 parts of sodium ethylenediaminetetraacetate (EDTA), and 0.24 parts of sodium formaldehyde sulfoxylate were added to initiate radical polymerization. After stirring for 1 hour and confirming the exothermic polymerization peak, the polymerization was completed by holding at 70°C for 1 hour to obtain a composite rubber latex.

[0180] The obtained composite rubber latex was heated to 75°C, and after adding the amount of initiator described in Table 1, graft polymerization was carried out by dropwise addition of a mixture of vinyl monomer components (b) and other components having the same composition as described in Table 1. After the addition was completed, the mixture was held at 75°C for 1 hour, then cooled to 25°C to obtain latex of composition (X-1) containing polymer (C-1). The solid content of the latex of composition (X-1) was 32%, and the polymerization rate was 99.9% or higher. This polymerization rate is the polymerization rate of the monomer components used in all processes from the manufacture of the composite rubber to graft polymerization. The number-average particle size (Dn) of the latex of composition (X-1) measured by a capillary particle size analyzer was 116 nm, the mass-average particle size (Dw) was 129 nm, and the Dw / Dn ratio was 1.11.

[0181] Next, 630 parts of an aqueous solution with a calcium acetate concentration of 0.8% were heated to 50°C, and while stirring, the latex of composition (X-1) was gradually added dropwise to this aqueous solution and allowed to solidify. The obtained composition (X-1) was filtered, washed, dehydrated, and then dried to obtain composition (X-1) containing polymer (C-1). The proportion of THF-insoluble matter in the obtained composition (X-1) was 96%. The weight-average molecular weight of the THF-soluble matter was 60,000. Furthermore, the amount of constituent units derived from aromatic vinyl monomers in the THF-soluble matter of composition (X-1) was 1.5% by mass of the total mass of composition (X-1). These results are shown in Table 1.

[0182] <Preparation of Resin Composition (Z-1)> The previously obtained composition (X-1), acrylic resin (PMMA), and colorant were blended in the ratios shown in Table 2 to obtain a mixture. The obtained mixture was supplied to a devolatile twin-screw extruder (manufactured by Shibaura Machinery Co., Ltd., product name "TEM-35B") heated to a barrel temperature of 260°C and kneaded to obtain pellet-shaped resin composition (Z-1). In order to evaluate the degree of yellowness during molding under molding condition 2, an uncolored mixture without colorant was melt-kneaded to obtain pellet-shaped resin composition (Z-1').

[0183] <Manufacturing of Molded Articles> A pellet-shaped resin composition (Z-1) was injection-molded under molding condition 1 to produce molded article A, measuring 80 mm in length, 10 mm in width, and 4 mm in thickness, and molded article B, measuring 100 mm in length, 50 mm in width, and 2 mm in thickness. Molded article A was used as test piece A for measuring Charpy impact strength and flexural modulus, and molded article B was used as test piece B for evaluating colored appearance. Various measurements and evaluations were performed. In addition, a pellet-shaped resin composition (Z-1') was injection-molded under molding condition 2 below to produce molded article B, measuring 100 mm in length, 50 mm in width, and 2 mm in thickness, and molded article B was used as test piece B for evaluating the degree of yellowing due to high temperature. The results are shown in Table 3.

[0184] (Molding conditions 1) - Injection molding machine: SE100DU (product name) manufactured by Sumitomo Heavy Industries, Ltd. - Cylinder temperature: 250℃, Mold temperature: 60℃ (Molding conditions 2) - Injection molding machine: SE100DU (product name) manufactured by Sumitomo Heavy Industries, Ltd. - Cylinder temperature: 280℃, Mold temperature: 80℃ - Residence time: 30 minutes Here, "residence time" is the time from when the pelletized resin composition (Z-1') is introduced into the injection molding machine and the resin is replaced until the injection molding process begins.

[0185] [Example 2] Composition (X-2) containing polymer (C-2) was produced in the same manner as in Example 1, except that the reactor capacity used for producing polymer (C-2) was 1000 liters. Various measurements were performed on composition (X-2). The results are shown in Table 1. Furthermore, pellet-shaped resin compositions (Z-2) and (Z-2') were produced in the same manner as in Example 1, except that the obtained composition (X-2) was used, and molded articles A and B were prepared, and various measurements and evaluations were performed. The results are shown in Table 3.

[0186] [Comparative Example 1] A composition (X-3) containing polymer (C-3) was prepared in the same manner as in Example 1, except that the amount of ferrous sulfate heptahydrate, a reducing agent used during polymerization, was 0.05 parts, the amount of ethylenediaminetetraacetate sodium (EDTA), a chelating agent, was 0.08 parts, and sodium formaldehyde sulfoxylate was not added. Various measurements were then performed. The results are shown in Table 1. Furthermore, pellet-shaped resin compositions (Z-3) and (Z-3') were prepared in the same manner as in Example 1, except that the obtained composition (X-3) was used. Molded articles A and B were then prepared, and various measurements and evaluations were performed. The results are shown in Table 3.

[0187] [Comparative Example 2] A composition (X-4) containing polymer (C-4) was prepared in the same manner as in Example 2, except that the amount of ferrous sulfate heptahydrate, a reducing agent used during polymerization, was 0.05 parts, the amount of ethylenediaminetetraacetate sodium (EDTA), a chelating agent, was 0.08 parts, and sodium formaldehyde sulfoxylate was not added. Various measurements were then performed. The results are shown in Table 2. Furthermore, pellet-shaped resin compositions (Z-4) and (Z-4') were prepared in the same manner as in Example 1, except that the obtained composition (X-4) was used. Molded articles A and B were then produced, and various measurements and evaluations were performed. The results are shown in Table 3.

[0188] [Comparative Example 3] An attempt was made to produce a polymer in the same manner as in Example 1, except that ferrous sulfate and sodium formaldehyde sulfoxylate, which are reducing agents, and sodium ethylenediaminetetraacetate (EDTA), which is a chelating agent, were not added during polymerization. However, the polymerization reaction did not start even after 5 hours, and no polymer was obtained.

[0189] [Comparative Examples 4-6] Except for changing the compositions of vinyl monomer component (a) and vinyl monomer component (b), the amount of sodium dodecylbenzenesulfonate (DBSNa), an emulsifier added during the polymerization of vinyl monomer component (a), and the amounts of potassium persulfate (KPS), a polymerization initiator, and n-octyl mercaptan (nOM), a chain transfer agent, used during the polymerization of vinyl monomer component (b), as shown in Table 2, and changing the amount of ferrous sulfate heptahydrate, a reducing agent used during polymerization, to 0.05 parts, and the amount of ethylenediaminetetraacetate sodium (EDTA), a chelating agent, to 0.08 parts, and not adding sodium formaldehyde sulfoxylate, compositions (X-5) containing polymer (C-5), composition (X-6) containing polymer (C-6), and composition (X-7) containing polymer (C-7) in the same manner as in Example 1, compositions (X-5) to (X-7) were prepared. Various measurements were performed on compositions (X-5) to (X-7). The results are shown in Table 2. Furthermore, pelletized resin compositions (Z-5) to (Z-7) were manufactured in the same manner as in Example 1, except that the obtained compositions (X-5) to (X-7) were used. Molded articles A and B were then produced, and various measurements and evaluations were performed. The results are shown in Table 3.

[0190]

[0191]

[0192]

[0193] The abbreviations in Tables 1-3 are as follows: nBA: n-butyl acrylate, AMA: allyl methacrylate, MMA: methyl methacrylate, AN: acrylonitrile, St: styrene, DBSNa: sodium dodecylbenzenesulfonate, KPS: potassium persulfate, nOM: n-octyl mercaptan, PMMA: polymer containing 90% or more of methyl methacrylate-derived structural units (manufactured by Mitsubishi Chemical Corporation, product name "Acrypet VH001"), OD-1: organic dye (manufactured by Mitsubishi Chemical Corporation, product name "Diarezin Green C"), OD-2: organic dye (manufactured by Mitsubishi Chemical Corporation, product name "Diarezin Red A"), OD-3: organic dye (manufactured by Mitsubishi Chemical Corporation, product name "Diarezin Blue G").

[0194] As is clear from the results shown in Table 3, Examples 1 and 2 exhibited excellent flexural modulus and colored appearance. Furthermore, they also demonstrated excellent impact strength and superior yellowing at high temperatures and retention periods (b*). Examples 1 and 2 can be said to have solved multiple problems simultaneously. On the other hand, Comparative Examples 1 and 2 were inferior in yellowing at high temperatures and retention periods (b*). Comparative Examples 4 and 6 were also inferior in colored appearance. Comparative Example 5 was inferior in both colored appearance and impact strength.

Claims

1. A composition comprising a polyorganosiloxane-containing polymer (C), wherein the composition contains a polymer soluble in tetrahydrofuran and a polymer insoluble in tetrahydrofuran, the content of constituent units derived from aromatic vinyl monomers in the tetrahydrofuran-soluble polymer is 3.5% by mass or less with respect to the total mass of the composition, the composition contains element Fe, the content of element Fe per 1 g of the composition is 1.58 μg / g or less, and the mass-average particle diameter of the composition is 150 nm or less.

2. The composition according to claim 1, wherein when the content of constituent units derived from aromatic vinyl monomers in the tetrahydrofuran-soluble polymer is α (mass%) relative to the total mass of the composition, and the content of element Fe per gram of the composition is β (μg / g), the ratio of α / β is 3 or more.

3. The composition according to claim 1 or 2, wherein the polyorganosiloxane-containing polymer (C) comprises a polymer (A) portion containing a polyorganosiloxane (A1) and a first vinyl polymer (A2), and a second vinyl polymer (B) portion.

4. The composition according to claim 3, wherein the content of the polymer (A) portion is 60% by mass or more and 95% by mass or less with respect to the total mass of the composition.

5. The composition according to claim 3 or 4, wherein the first vinyl polymer (A2) is a polymer of a vinyl monomer component (a2), and the vinyl monomer component (a2) comprises a (meth)acrylate monomer.

6. The composition according to any one of claims 3 to 5, wherein the second vinyl polymer (B) portion is a polymer of vinyl monomer component (b), and the vinyl monomer component (b) comprises a (meth)acrylate monomer and an aromatic vinyl monomer.

7. The composition according to claim 6, wherein the total content of the (meth)acrylate monomer and the aromatic vinyl monomer in the vinyl monomer component (b) is 50% by mass or more with respect to the total mass of the vinyl monomer component (b).

8. The composition according to claim 6 or 7, wherein the vinyl monomer component (b) contains methyl methacrylate, and the content of methyl methacrylate is 10% by mass or more with respect to the total mass of the vinyl monomer component (b).

9. The composition according to any one of claims 3 to 8, wherein the polymer (A) portion 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).

10. The composition according to any one of claims 3 to 9, wherein the content of the polyorganosiloxane (A1) is 1% by mass or more and 50% by mass or less based on the total mass of the composition.

11. The composition according to any one of claims 3 to 9, wherein the content of the polyorganosiloxane (A1) is 1% by mass or more and 10% by mass or less based on the total mass of the composition.

12. A resin composition comprising the composition according to any one of claims 1 to 11 and a thermoplastic resin other than the said composition.

13. A molded article comprising the resin composition described in claim 12.

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