Resin composition, its manufacturing method, and molded article using the same

Abstract

To provide a resin composition which is excellent in impact resistance and tensile elongation, in which deterioration of appearance (fish eyes, glossiness) caused by aggregation of rubbery polymers is suppressed, and which has good color development properties. [Solution] A graft copolymer (A) is obtained by graft copolymerizing a monomer mixture (a) containing at least an aromatic vinyl monomer (a1) and a vinyl cyanide monomer (a2) in the presence of a rubber polymer (r), and a vinyl copolymer (B) is obtained by copolymerizing a monomer mixture (b) containing at least an aromatic vinyl monomer (b1) and a vinyl cyanide monomer (b2). The graft copolymer (A) contains specific amounts of either or both of a specific phosphate ester compound (E1) and a polyoxyethylene alkylamine (E2).

Description

[Technical Field]

[0001] The present invention relates to a resin composition useful for resin molded articles used in home electric appliances, communication-related devices, general merchandise, automotive materials, and the like. [Background technology]

[0002] Styrenic thermoplastic resin compositions containing rubbery polymers, such as ABS (acrylonitrile-butadiene-styrene) resin, offer excellent balance of mechanical strength, such as impact resistance and rigidity, as well as moldability. On the other hand, styrenic thermoplastic resin compositions containing rubbery polymers, such as ASA (acrylonitrile-styrene-acrylate) resin, contain saturated acrylic rubber, which is stable against ultraviolet light, and can provide excellent weather resistance. These thermoplastic resins are widely used in a variety of fields, including home appliances, general merchandise, and automotive materials.

[0003] On the other hand, ABS resins tend to suffer from a deterioration in appearance due to aggregation of rubbery polymers, while ASA resins tend to suffer from a deterioration in appearance and color development due to aggregation of rubbery polymers.

[0004] The following methods have been proposed as techniques for improving the surface appearance (color tone, fisheyes) of molded articles. For example, Patent Document 1 proposes a method for producing a rubber-modified thermoplastic resin, which comprises polymerizing a monomer component consisting of 6 to 63% by weight of an aromatic vinyl compound (b) and 2 to 49% by weight of a vinyl cyanide compound (c) [where (a) + (b) + (c) = 100% by weight] in the presence of 30 to 80% by weight of a rubber-like polymer (a), using a mercaptopropionic acid alkyl ester having a specific structure as a molecular weight modifier. For example, Patent Document 2 proposes a rubber-modified thermoplastic resin obtained by polymerizing a vinyl monomer (b) in the presence of a rubber-like polymer (a), wherein the component (a) accounts for 40 to 80% by weight of the total of the components (a) and (b), the component (b) comprises an aromatic vinyl compound (b1), a vinyl cyanide compound (b2), and a (meth)acrylic acid ester compound (b3), the (meth)acrylic acid ester compound (b3) being a monomer that exhibits a glass transition temperature (Tg) of 0°C or lower when forming a homopolymer, and accounting for 0.1 to 20% by weight of the total of the component (b).

[0005] On the other hand, styrene-based thermoplastic resin compositions containing heat-resistant vinyl copolymers have been widely used in automotive materials, particularly lamp housings, due to the excellent heat resistance of their molded products. Lamp housings are typically subjected to secondary processing, such as painting, metal vapor deposition, and plating, to enhance the brightness of vehicle lamps. To achieve a beautiful appearance after secondary processing, the surface of the molded product prior to secondary processing must be highly smooth. To achieve a smooth surface, molded products typically undergo undercoating. A smooth molded product allows for direct formation of a metal layer without forming an undercoat layer, thereby reducing product costs. A method for forming a metal layer that omits the formation of an undercoat layer, known as the "direct vapor deposition method," has become common in recent years. Therefore, resin compositions used to form lamp housings and other components are required to produce molded products with excellent smoothness.

[0006] The following methods have been proposed as techniques for imparting impact resistance, heat resistance, molded product appearance, and vibration weldability to thermoplastic resin compositions for lamp housings. For example, Patent Document 3 discloses a composite rubber-reinforced graft resin obtained by polymerizing vinyl monomers including an aromatic vinyl compound and a vinyl cyanide compound in the presence of [A] an acrylic rubber-like polymer (a1) having a gel content of 70% by mass or more, a degree of swelling with toluene of 5.5 to 30 times, a volume average particle size of 100 to 200 nm, and a ratio of the volume average particle size to the number average particle size of less than 1.1; [B] an organosiloxane rubber, and a composite rubber (b1) containing a (co)polymer rubber having structural units derived from a (meth)acrylic acid alkyl ester, and vinyl monomers including a (meth)acrylic acid alkyl ester, the glass transition temperature of which of the homopolymer exceeds 0°C; and a maleimide-based copolymer [C] containing 10 to 70% by mass of structural units derived from a maleimide-based compound relative to the preceding structural units, and a composite rubber (b1) containing structural units derived from an aromatic vinyl compound, structural units derived from a vinyl cyanide compound, and a polymer [D] containing at least one structural unit selected from structural units derived from (meth)acrylic acid alkyl esters and not containing any structural units derived from maleimide-based compounds, wherein the total content of the acrylic rubbery polymer (a1) and the composite rubber (b1) is 8 to 35 mass % when the total of the acrylic rubbery polymer-reinforced graft resin [A], the composite rubber-reinforced graft resin [B], the maleimide-based copolymer [C], and the polymer [D] is taken as 100 mass %, and the content of structural units derived from maleimide-based compounds is 5 to 30 mass % when the total of the structural units constituting the acrylic rubbery polymer-reinforced graft resin [A], the structural units constituting the composite rubber-reinforced graft resin [B], the structural units constituting the maleimide-based copolymer [C], and the structural units constituting the polymer [D] is taken as 100 mass %.Patent Document 4 describes a thermoplastic resin composition containing the following graft copolymer (A), graft copolymer (B), copolymer (C), and copolymer (D), wherein the mass ratio ((A):(B)) of graft copolymer (A) to graft copolymer (B) is 50:50 to 80:20, the total content of rubber derived from graft copolymer (A) and graft copolymer (B) contained in the thermoplastic resin composition is 10 to 30 mass%, the content of structural units derived from conjugated diene rubber is less than 2 mass%, and the thermoplastic resin composition contains 10 to 30 parts by mass of copolymer (C) (where the total of graft copolymer (A), graft copolymer (B), copolymer (C), and copolymer (D) is 100 parts by mass). Graft copolymer (A): An acrylic rubber-based graft copolymer obtained by graft polymerizing a monomer component containing at least one monomer selected from an aromatic vinyl monomer and a vinyl cyanide monomer onto an acrylic rubber-based polymer (rs) having a volume average particle size of 70 to 200 nm, which is obtained by polymerizing 0 to 20 mass% of polyorganosiloxane and 80 to 100 mass% of alkyl (meth)acrylate monomer (where the total of polyorganosiloxane and alkyl (meth)acrylate monomer is 100 mass%). Graft copolymer (B): An acrylic rubber-based graft copolymer obtained by graft polymerizing a monomer component containing at least one monomer selected from an aromatic vinyl monomer and a vinyl cyanide monomer onto an acrylic rubber-based polymer (r1) having a volume average particle size of 300 to 600 nm, the polymer being obtained by polymerizing 0 to 30% by mass of a conjugated diene rubber-based polymer and 70 to 100% by mass of an alkyl (meth)acrylate monomer (where the total of the conjugated diene rubber-based polymer and the alkyl (meth)acrylate monomer is 100% by mass). Copolymer (C): A copolymer containing 10 to 65% by mass of maleimide-based monomer units out of 100% by mass of all monomer units constituting copolymer (C), and having a reduced viscosity of 0.4 to 0.7 dl / g in N,N-dimethylformamide solution at 25°C. Copolymer (D): A monomer component containing at least one monomer selected from the group consisting of an aromatic vinyl monomer and a vinyl cyanide monomer (but not including a maleimide monomer).A copolymer obtained by polymerizing and having a reduced viscosity of 0.4 to 0.7 dl / g in an N,N-dimethylformamide solution at 25°C has been proposed.

[0007] Furthermore, the following method has been proposed as a technique for providing an emulsion polymerization latex of a polymer capable of forming a resin molded body excellent in productivity during melt extrusion and having a good appearance. For example, Patent Document 5 proposes a method for producing an emulsion polymerization latex, which includes an emulsion polymerization step using an emulsifier containing phosphoric acid and a phosphate ester salt having a specific structure, and the content of the phosphoric acid is 15,000 ppm or less.

[0008] The following method has been proposed as a technique for imparting antistatic properties, transparency, and suitability for water-based ink printing to a polyolefin resin composition. For example, Patent Document 6 proposes a polyolefin resin composition containing 0.05 to 2.00% by weight of a polyoxyethylene alkylamine or polyoxyethylene alkenylamine having a specific structure, which can be obtained by adding X moles of ethylene oxide in the range of 2 < X ≤ 10 to 1 mole of an alkylamine or alkenylamine having 8 to 22 carbon atoms.

[0009] However, in any of these techniques, there are problems such as deterioration of appearance (fish eyes, glossiness) caused by aggregation of the rubbery polymer, and insufficient improvement in color development, which may limit the application to a wide range of uses.

Prior Art Documents

Patent Documents

[0010]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

[0011] The present invention aims to solve the problems in the prior art described above, that is, to provide a resin composition that has good color development properties while maintaining impact resistance and high tensile elongation and eliminating the deterioration in appearance (fish eyes, glossiness) caused by aggregation of rubber polymers. [Means for solving the problem]

[0012] As a result of intensive research conducted by the present inventors to achieve the above object, it was found that when a resin composition containing a vinyl copolymer obtained by copolymerizing a vinyl monomer mixture and a rubber polymer-containing graft copolymer, preferably a heat-resistant vinyl copolymer, is blended with specific amounts of either or both of a phosphate ester compound having a specific structure and a polyoxyethylene alkylamine having a specific structure, the deterioration of appearance (fish eyes, gloss) caused by aggregation of the rubber polymer can be eliminated and a resin composition with good color development can be obtained, thereby completing the present invention. That is, one aspect of the present invention is as follows. (1) A resin composition comprising: a graft copolymer (A) obtained by graft copolymerizing a monomer mixture (a) containing at least an aromatic vinyl monomer (a1) and a vinyl cyanide monomer (a2) in the presence of a rubbery polymer (r); a vinyl copolymer (B) obtained by copolymerizing a monomer mixture (b) containing at least an aromatic vinyl monomer (b1) and a vinyl cyanide monomer (b2); and either or both of a phosphate ester compound (E1) represented by the following chemical formula (1) and a polyoxyethylene alkylamine (E2) represented by the following chemical formula (2), and the total amount of the phosphate ester compound (E1) and the polyoxyethylene alkylamine (E2) is contained at a ratio of 60 ppm (mass / mass) or more based on the total amount of the entire resin composition.

[0013] [Chemical formula]

[0014] (Here, R is an alkyl group or alkenyl group having 8 to 22 carbon atoms, AO is an oxyalkylene group having 2 or 3 carbon atoms, n is an integer of 1 to 20, m is an integer of 1 or 2, M is a hydrogen atom, a Group 1 metal atom or a Group 2 metal atom, and q is 1 when M is a hydrogen atom or a Group 1 metal atom, and 1 / 2 when M is a Group 2 metal atom.)

[0015] [Chemical formula]

[0016] (Here, R represents an alkyl group or alkenyl group having 8 to 22 carbon atoms, and m and n are positive integers satisfying the relationship 2 < m + n ≤ 20.) (2) a step of obtaining an emulsion-polymerized latex by graft copolymerizing a monomer mixture (a) containing at least an aromatic vinyl monomer (a1) and a vinyl cyanide monomer (a2) in the presence of a rubber polymer (r), a step of adding either or both of a phosphoric acid ester compound (E1) and a polyoxyethylene alkylamine (E2) to the emulsion-polymerized latex, and then a step of contacting the emulsion-polymerized latex with an aqueous sulfuric acid solution to obtain a graft copolymer (A) (Step A); a step (step B) of obtaining a vinyl copolymer (B) obtained by copolymerizing a monomer mixture (b) containing at least an aromatic vinyl monomer (b1) and a vinyl cyanide monomer (b2); a step (step C) of obtaining a heat-resistant vinyl copolymer (C) obtained by copolymerizing a vinyl monomer mixture (c) containing at least an aromatic vinyl monomer (c1) and a maleimide monomer (c2) as necessary; a step of mixing the graft copolymer (A), the vinyl copolymer (B), and the heat-resistant vinyl copolymer (C) obtained in the steps A, B, and C (provided that the heat-resistant vinyl copolymer (C) is an optional component), A method for producing a resin composition, characterized by adjusting the total amount of a phosphate ester compound (E1) and a polyoxyethylene alkylamine (E2) to be 60 ppm (mass / mass) or more relative to the total amount of the entire resin composition. [Effects of the Invention]

[0017] According to the present invention, it is possible to obtain a resin composition that has excellent impact resistance and high tensile elongation, that eliminates deterioration in appearance (fish eyes, glossiness) caused by aggregation of rubber polymers, and that has excellent color development properties. [Brief explanation of the drawings]

[0018] [Figure 1] Transmission electron microscope (TEM) image of the resin composition produced by the method described in Example 14 [Figure 2] Transmission electron microscope (TEM) image of the resin composition produced by the method described in Comparative Example 7

Mode for Carrying Out the Invention

[0019] The resin composition of the present invention contains at least the following components. Component 1: A graft copolymer (A) obtained by graft copolymerizing a monomer mixture (a) containing at least an aromatic vinyl monomer (a1) and a vinyl cyanide monomer (a2) in the presence of a rubbery polymer (r). Component 2: A vinyl copolymer (B) obtained by copolymerizing a monomer mixture (b) containing at least an aromatic vinyl monomer (b1) and a vinyl cyanide monomer (b2). Component 3: Either or both of a phosphate ester compound (E1) represented by the following chemical formula (1) and a polyoxyethylene alkylamine (E2) represented by the following chemical formula (2).

[0020]

Chemical formula

[0021] (R is an alkyl group or alkenyl group having 8 to 22 carbon atoms, AO is an oxyalkylene group having 2 or 3 carbon atoms, n is an integer of 1 to 20, m is an integer of 1 or 2, M is a hydrogen atom, a Group 1 metal atom or a Group 2 metal atom, and q is 1 when M is a hydrogen atom or a Group 1 metal atom, and 1 / 2 when M is a Group 2 metal atom.)

[0022]

Chemical formula

[0023] (Here, R represents an alkyl group or alkenyl group having 8 to 22 carbon atoms, and m and n are positive integers satisfying the relationship 2 < m + n ≤ 20.) Also, it can preferably contain the following components. Component 4: A heat-resistant vinyl copolymer (C) obtained by copolymerizing a vinyl monomer mixture (c) containing at least an aromatic vinyl monomer (c1) and a maleimide monomer (c2).

[0024] Furthermore, as will be described later, the resin composition of the present invention may contain other components as necessary.

[0025] Although the function of each component in the resin composition of the present invention is not entirely clear, the inventors understand it as follows. Specifically, the graft copolymer (A) can improve the moldability of the resin composition, reduce the volatility of the molded article, and improve the impact resistance and tensile elongation of the molded article. Furthermore, the vinyl copolymer (B) can improve the fluidity of the resin composition, enhance the appearance of the molded article, and improve the color development. Furthermore, the phosphate ester compound (E1) and the polyoxyethylene alkylamine (E2) can improve the appearance of the molded article and improve the color development and tensile elongation of the molded article. Furthermore, the heat-resistant vinyl copolymer (C) can impart heat resistance to the molded article.

[0026] Each component will be listed and explained in more detail below.

[0027] Component 1: Graft copolymer (A) The graft copolymer (A) used in the present invention is obtained by graft copolymerizing a monomer mixture (a) containing at least an aromatic vinyl monomer (a1) and a vinyl cyanide monomer (a2) in the presence of a rubbery polymer (r). The vinyl monomer mixture (a) may further contain other monomers copolymerizable with (a1) to (a2), which will be described later.

[0028] Examples of the rubbery polymer (r) include polybutadiene, poly(butadiene-styrene) (SBR), polybutyl acrylate (acrylic rubber), poly(butadiene-butyl acrylate), poly(butadiene-methyl methacrylate), poly(butyl acrylate-methyl methacrylate), poly(butadiene-ethyl acrylate), and natural rubber. Two or more of the above materials may be used as the rubbery polymer (r). Among the rubbery polymers (r), polybutadiene, acrylic rubber, SBR, and natural rubber are preferred, with polybutadiene and acrylic rubber being more preferred, from the viewpoint of further improving impact resistance, transparency, and color tone.

[0029] The content of the rubbery polymer (r) is preferably 20% by mass or more and 80% by mass or less relative to the total amount of the rubbery polymer (r) and the vinyl monomer mixture (a) constituting the graft copolymer (A). If the content of the rubbery polymer (r) is 20% by mass or more, the impact resistance of the molded article can be further improved. The content of the rubbery polymer (r) is more preferably 35% by mass or more. On the other hand, if the content of the rubbery polymer (r) is 80% by mass or less, the fluidity of the final resin composition, and the impact resistance, appearance, and color development of the molded article can be further improved. The content of the rubbery polymer (r) is more preferably 60% by mass or less.

[0030] The volume average particle diameter of the rubbery polymer (r) is preferably 0.08 μm or more, more preferably 0.10 μm or more, and is preferably 0.40 μm or less, more preferably 0.35 μm or less. By making the volume average particle diameter of the rubbery polymer (r) 0.08 μm or more, it is possible to suppress a decrease in the impact resistance of a molded article. Furthermore, by making the volume average particle diameter of the rubbery polymer (r) 0.40 μm or less, it is possible to suppress a decrease in the fluidity of the final resin composition, and in the appearance and color development of the molded article.

[0031] In particular, when polybutadiene is used as the rubbery polymer (r), the volume average particle diameter of the polybutadiene is preferably 0.2 μm or more and 0.35 μm or less, from the viewpoints of relatively good rubber dispersibility and improving the impact resistance of the molded article without deteriorating the appearance and color development of the molded article. Also, when acrylic rubber is used as the rubbery polymer (r), the volume average particle diameter of the acrylic rubber is preferably 0.08 μm or more and 0.20 μm or less, from the viewpoints of suppressing a decrease in the impact resistance of the molded article and maintaining the appearance and color development of the molded article, since the rubber is relatively prone to aggregation.

[0032] Polybutadiene is a synthetic rubber known to have butadiene as its main component, and known materials can be used without particular limitations. The acrylic rubber is a synthetic rubber known to have acrylic ester as its main component, and known materials can be used without particular limitations. For example, an acrylic rubber polymer described in a known document (JP 2016-176971 A) can be used.

[0033] Examples of the aromatic vinyl monomer (a1) in the vinyl monomer mixture (a) include styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, o-methylstyrene, vinyltoluene, and t-butylstyrene. Two or more of these may be contained as the aromatic vinyl monomer (a1). Among the aromatic vinyl monomers (a1), styrene is preferred from the viewpoint of further improving the flowability of the final resin composition and the rigidity of the molded article.

[0034] The content of the aromatic vinyl monomer (a1) in the vinyl monomer mixture (a) is preferably 60% by mass or more, more preferably 65% ​​by mass or more, and even more preferably 70% by mass or more, based on 100% by mass of the total vinyl monomer mixture (a), from the viewpoint of further improving the flowability of the final resin composition and the rigidity of the molded article. On the other hand, the content of the aromatic vinyl monomer (a1) in the vinyl monomer mixture (a) is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, from the viewpoint of improving the impact resistance of the molded article.

[0035] Examples of the vinyl cyanide monomer (a2) in the vinyl monomer mixture (a) include acrylonitrile, methacrylonitrile, and ethacrylonitrile. Two or more of these may be contained as the vinyl cyanide monomer (a2). Among the vinyl cyanide monomers (a2), acrylonitrile is preferred from the viewpoint of further improving the impact resistance of the molded article.

[0036] The content of the vinyl cyanide monomer (a2) in the vinyl monomer mixture (a) is preferably 20% by mass or more, more preferably 25% by mass or more, and even more preferably 30% by mass or more, based on 100% by mass of the total vinyl monomer mixture (a), from the viewpoint of improving the impact resistance of the molded article. On the other hand, the content of the vinyl cyanide monomer (a2) in the vinyl monomer mixture (a) is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, from the viewpoint of improving the flowability of the final resin composition and the color tone of the molded article.

[0037] The other monomer copolymerizable with the aromatic vinyl monomer (a1) and the vinyl cyanide monomer (a2) is not particularly limited as long as it is a vinyl monomer other than the aromatic vinyl monomer (a1) and the vinyl cyanide monomer (a2) and does not impair the effects of the present invention. Specific examples of the other monomer include (meth)acrylic acid ester monomer (a3), unsaturated fatty acid, acrylamide monomer, and maleimide monomer, and two or more of these may be contained.

[0038] The (meth)acrylic acid ester monomer (a3) ​​that can be contained in the vinyl monomer mixture (a) is preferably, for example, an ester of a C1-6 alcohol with acrylic acid or methacrylic acid. The ester of a C1-6 alcohol with acrylic acid or methacrylic acid may further have a substituent such as a hydroxyl group or a halogen group. Examples of the ester of a C1-6 alcohol with acrylic acid or methacrylic acid include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, chloromethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2,3,4,5,6-pentahydroxyhexyl (meth)acrylate, and 2,3,4,5-tetrahydroxypentyl (meth)acrylate. Two or more of these may be contained as the (meth)acrylic acid ester monomer (a2). Among the (meth)acrylic acid ester monomers (a2), methyl (meth)acrylate is preferred from the viewpoint of improving the color development of the molded article. In this specification, "(meth)acrylic acid" means both acrylic acid and methacrylic acid, and for example, methyl (meth)acrylate means both methyl methacrylate and methyl acrylate.

[0039] The content of the (meth)acrylic acid ester monomer (a3) ​​in the vinyl monomer mixture (a) is preferably 30% by mass or more, more preferably 50% by mass or more, and even more preferably 70% by mass or more, based on 100% by mass of the total vinyl monomer mixture (a), from the viewpoint of improving the color development of the molded article. On the other hand, the content of the (meth)acrylic acid ester monomer (a2) in the vinyl monomer mixture (a) is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less, from the viewpoint of further improving the impact resistance of the molded article.

[0040] Examples of unsaturated fatty acids include itaconic acid, maleic acid, fumaric acid, butenoic acid, acrylic acid, and methacrylic acid. Examples of acrylamide monomers include acrylamide, methacrylamide, and N-methylacrylamide. Examples of maleimide monomers include N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-dodecylmaleimide, N-cyclohexylmaleimide, and N-phenylmaleimide.

[0041] The weight-average molecular weight of the solvent-soluble portion of the graft copolymer (A) is not particularly limited, but is preferably 50,000 or more, more preferably 60,000 or more. If the weight-average molecular weight of the solvent-soluble portion of the graft copolymer (A) is 50,000 or more, the impact resistance of the molded article can be further improved. On the other hand, the weight-average molecular weight of the solvent-soluble portion of the graft copolymer (A) is preferably 120,000 or less, more preferably 100,000 or less. If the weight-average molecular weight of the solvent-soluble portion of the graft copolymer (A) is 120,000 or less, the fluidity of the final resin composition can be further improved.

[0042] Here, the weight-average molecular weight of the solvent-soluble portion of the graft copolymer (A) is determined by filtering the solvent-insoluble portion from the graft copolymer (A), concentrating the filtrate using a rotary evaporator, and then dissolving approximately 0.03 g of the solvent-soluble portion in approximately 15 g of tetrahydrofuran to prepare a solution of approximately 0.2 mass%. The weight-average molecular weight can be determined from a GPC chromatogram measured using this solution, using polystyrene as the standard. The GPC measurement can be performed under the following conditions. When determining the solvent-soluble portion, acetone is used as the solvent when polybutadiene rubber is used as the rubbery polymer (r), and acetonitrile is used as the solvent when acrylic rubber is used as the rubbery polymer (r). In particular, when using a rubbery polymer containing butadiene or natural rubber among the examples of the rubbery polymer (r), acetone is used as the solvent, while when using a rubbery polymer primarily composed of an acrylic ester, such as poly(butyl acrylate-methyl methacrylate), acetonitrile is used as the solvent. When a rubber polymer not exemplified above is used as the rubber polymer (r), acetone is used as the solvent. Measurement equipment: Waters2695 Column temperature: 40℃ Detector: RI2414 (differential refractometer) Carrier eluent flow rate: 0.3 ml / min (solvent: tetrahydrofuran) Columns: TSKgel SuperHZM-M (6.0 mm I.D. x 15 cm) and TSKgel SuperHZM-N (6.0 mm I.D. x 15 cm) in series (both manufactured by Tosoh Corporation).

[0043] The graft ratio of the graft copolymer (A) is not particularly limited, but from the viewpoint of improving the impact resistance, appearance, and color development of the molded article, it is preferably 10% or more and 100% or less, and more preferably 30% or more and 60% or less.

[0044] The graft ratio of the graft copolymer (A) can be determined by the following method. First, 80 ml of solvent is added to approximately 1 g of the graft copolymer (A) and refluxed in a 70°C water bath for 3 hours. This solution is centrifuged at 8,000 rpm (10,000 G) for 40 minutes, and the insoluble matter is filtered to obtain a solvent-insoluble matter. The obtained solvent-insoluble matter is dried under reduced pressure at 80°C for 5 hours, and its mass (referred to as n in the formula below) is measured, and the graft ratio is calculated using the formula below. Here, m is the mass of the sample of graft copolymer (A) used, and X is the rubber polymer content (mass%) of the graft copolymer (A). Grafting rate (%) = {[(n) - ((m) × X / 100)] / [(m) × X / 100]} × 100.

[0045] In determining the graft ratio, acetone is used as the solvent when polybutadiene rubber is used as the rubber polymer (r), and acetonitrile is used as the solvent when acrylic rubber is used as the rubber polymer (r). In particular, when using a rubber polymer containing butadiene or natural rubber among the examples of the rubber polymer (r), acetone is used as the solvent, and when using a rubber polymer having an acrylic acid ester as the main component, such as poly(butyl acrylate-methyl methacrylate), acetonitrile is used as the solvent. Furthermore, when using a rubber polymer not listed as an example of the rubber polymer (r), acetone is used as the solvent.

[0046] The method for producing the graft copolymer (A) is preferably an emulsion polymerization method, since the particle size of the rubbery polymer (r) can be easily adjusted to the desired range and the polymerization stability can be easily adjusted by removing heat during polymerization.

[0047] When the graft copolymer (A) is produced by emulsion polymerization, the method for charging the rubber polymer (r) and the vinyl monomer mixture (a) is not particularly limited. For example, they may all be charged at once at the initial stage, or a portion of the vinyl monomer mixture (a) may be continuously charged to adjust the copolymer composition distribution. Alternatively, some or all of the vinyl monomer mixture (a) may be charged in portions. Here, "continuously charging a portion of the vinyl monomer mixture (a)" means that a portion of the vinyl monomer mixture (a) is initially charged and the remainder is continuously charged over time. "Charging the vinyl monomer mixture (a) in portions" means that the vinyl monomer mixture (a) is charged at a later time than the initial charge.

[0048] When the graft copolymer (A) is produced by emulsion polymerization, various surfactants may be added as emulsifiers. As various surfactants, anionic surfactants such as carboxylate, sulfate, and sulfonate types are particularly preferred, and two or more types of anionic surfactants may be combined. Examples of salts include alkali metal salts such as sodium salts, lithium salts, and potassium salts, and ammonium salts.

[0049] Examples of carboxylate-type emulsifiers include caprylate, caprate, laurate, myristylates, palmitate, stearate, oleate, linoleate, linolenate, rosinate, behenate, and dialkyl sulfosuccinate.

[0050] Examples of sulfate type emulsifiers include castor oil sulfate, lauryl alcohol sulfate, polyoxyethylene lauryl sulfate, polyoxyethylene alkyl ether sulfate, and polyoxyethylene alkyl phenyl ether sulfate.

[0051] Examples of sulfonate-type emulsifiers include dodecylbenzenesulfonate, alkylnaphthalenesulfonate, alkyldiphenyletherdisulfonate, and naphthalenesulfonate condensates.

[0052] Among these, it is preferable to add a carboxylate-type emulsifier from the viewpoint of reducing the volatility of the molded product.

[0053] When the graft copolymer (A) is produced by emulsion polymerization, an initiator may be added as needed. Examples of initiators include peroxides, azo compounds, and water-soluble potassium persulfate, and two or more of these may be used in combination. A redox polymerization initiator may also be used as the initiator.

[0054] Examples of peroxides include benzoyl peroxide, cumene hydroperoxide, dicumyl peroxide, diisopropylbenzene hydroperoxide, t-butyl hydroperoxide, t-butyl peroxyacetate, t-butyl peroxybenzoate, t-butyl isopropyl carbonate, di-t-butyl peroxide, t-butyl peroxyoctate, 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, t-butylperoxy-2-ethylhexanoate, etc. Among the peroxides, cumene hydroperoxide, 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane, and 1,1-bis(t-butylperoxy)cyclohexane are particularly preferably used.

[0055] Examples of azo compounds include azobisisobutyronitrile, azobis(2,4-dimethylvaleronitrile), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2-cyano-2-propylazoformamide, 1,1'-azobiscyclohexane-1-carbonitrile, azobis(4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2'-azobisisobutyrate, 1-t-butylazo-2-cyanobutane, and 2-t-butylazo-2-cyano-4-methoxy-4-methylpentane. Among azo compounds, 1,1'-azobiscyclohexane-1-carbonitrile is particularly preferably used. The amount of initiator added to produce the graft copolymer (A) is not particularly limited, but from the viewpoint of easily adjusting the weight average molecular weight of the solvent-soluble portion of the graft copolymer (A) to the above-mentioned range, it is preferably 0.1 parts by mass or more and 0.5 parts by mass or less per 100 parts by mass of the total of the rubber polymer (r) and the vinyl monomer mixture (a).

[0056] A chain transfer agent may be used when producing the graft copolymer (A). By using the chain transfer agent, the weight-average molecular weight and graft ratio of the solvent-soluble portion of the graft copolymer (A) can be easily adjusted to the desired range. Examples of the chain transfer agent include (i) mercaptans such as n-octyl mercaptan, t-dodecyl mercaptan, n-dodecyl mercaptan, n-tetradecyl mercaptan, and n-octadecyl mercaptan, and (ii) terpenes such as terpinolene. Two or more of these may be used in combination. Among the chain transfer agents, n-octyl mercaptan and t-dodecyl mercaptan are preferred.

[0057] The amount of the chain transfer agent used to produce the graft copolymer (A) is not particularly limited. From the viewpoint of easily adjusting the weight average molecular weight and graft ratio of the solvent-soluble portion of the graft copolymer (A) to the above-mentioned ranges, the amount of the chain transfer agent used to produce the graft copolymer (A) is preferably 0.2 parts by mass or more, more preferably 0.4 parts by mass or more, and preferably 0.7 parts by mass or less, more preferably 0.6 parts by mass or less, per 100 parts by mass of the rubber polymer (r) and the vinyl monomer mixture (a) in total.

[0058] When the graft copolymer (A) is produced by emulsion polymerization, the polymerization temperature is not particularly limited. However, from the viewpoint of easily adjusting the weight average molecular weight of the solvent-soluble portion of the graft copolymer (A) to the above-mentioned range and from the viewpoint of emulsion stability, a temperature of 40°C or higher and 70°C or lower is preferred.

[0059] When the graft copolymer (A) is produced by emulsion polymerization, it is common to add a coagulant to the graft copolymer latex to recover the graft copolymer (A). As the coagulant, an acid or a water-soluble salt is preferably used.

[0060] Examples of acids used as coagulants include sulfuric acid, hydrochloric acid, phosphoric acid, and acetic acid. Examples of water-soluble salts used as coagulants include calcium chloride, magnesium chloride, barium chloride, aluminum chloride, magnesium sulfate, aluminum sulfate, ammonium aluminum sulfate, potassium aluminum sulfate, and sodium aluminum sulfate, and two or more of these may be combined. From the viewpoint of reducing the volatility of the molded product, it is preferable not to leave an emulsifier in the final resin composition of the present invention. For this reason, it is preferable to use a carboxylate-type emulsifier as the emulsifier, perform acid coagulation, and then neutralize with an alkali such as sodium hydroxide to remove the emulsifier.

[0061] Component 2: Vinyl copolymer (B) The vinyl copolymer (B) used in the resin composition of the present invention is obtained by copolymerizing a monomer mixture (b) containing at least an aromatic vinyl monomer (b1) and a vinyl cyanide monomer (b2). The vinyl monomer mixture (b) may further contain other monomers copolymerizable with the aromatic vinyl monomer (b1) and the vinyl cyanide monomer (b2). However, the vinyl monomer mixture (b) does not contain a maleimide monomer.

[0062] Examples of the aromatic vinyl monomer (b1) in the vinyl monomer mixture (b) include those exemplified as the aromatic vinyl monomer (a1), with styrene being preferred.

[0063] The content of the aromatic vinyl monomer (b1) in the vinyl monomer mixture (b) is preferably 60% by mass or more, more preferably 65% ​​by mass or more, and even more preferably 70% by mass or more, based on 100% by mass of the vinyl monomer mixture (b) in order to improve the flowability of the final resin composition and the rigidity of the molded article. On the other hand, the content of the aromatic vinyl monomer (b1) in the vinyl monomer mixture (b) is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, based on 100% by mass of the vinyl monomer mixture (b) in order to improve the impact resistance of the molded article.

[0064] Examples of the vinyl cyanide monomer (b2) in the vinyl monomer mixture (b) include those exemplified as the vinyl cyanide monomer (a2), with acrylonitrile being preferred.

[0065] The content of the vinyl cyanide monomer (b2) in the vinyl monomer mixture (b) is preferably 20% by mass or more, more preferably 25% by mass or more, and even more preferably 30% by mass or more, based on 100% by mass of the total vinyl monomer mixture (b), from the viewpoint of improving the impact resistance of the molded article. On the other hand, the content of the vinyl cyanide monomer (b2) in the vinyl monomer mixture (b) is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, based on 100% by mass of the total vinyl monomer mixture (b), from the viewpoint of improving the flowability of the final resin composition and the color tone of the molded article.

[0066] The other monomer copolymerizable with the aromatic vinyl monomer (b1) and the vinyl cyanide monomer (b2) is not particularly limited as long as it is a vinyl monomer other than the aromatic vinyl monomer (b1) and the vinyl cyanide monomer (b2) and does not impair the effects of the present invention. Specific examples of the other monomer include (meth)acrylic acid ester monomer (b3), unsaturated fatty acid, and acrylamide monomer, and two or more of these may be contained. However, the vinyl monomer mixture (b) does not include maleimide monomers. Examples of unsaturated fatty acids include itaconic acid, maleic acid, fumaric acid, butenoic acid, acrylic acid, and methacrylic acid. Examples of acrylamide monomers include acrylamide, methacrylamide, and N-methylacrylamide.

[0067] The weight-average molecular weight of the vinyl copolymer (B) is preferably 70,000 or more, more preferably 80,000 or more. By making the weight-average molecular weight of the vinyl copolymer (B) 70,000 or more, the impact resistance of the molded article can be further improved. On the other hand, the weight-average molecular weight of the vinyl copolymer (B) is preferably 200,000 or less, more preferably 150,000 or less. By making the weight-average molecular weight of the vinyl copolymer (B) 200,000 or less, the fluidity of the final resin composition can be further improved. A vinyl copolymer (B) having a weight-average molecular weight in the range of 70,000 to 200,000 can be easily produced, for example, by using an initiator or chain transfer agent described below, or by setting the polymerization temperature in the preferred range described below.

[0068] Here, the weight average molecular weight of the vinyl copolymer (B) can be determined by converting the GPC chromatogram measured using a solution of about 0.2 mass % obtained by dissolving about 0.03 g of the vinyl copolymer (B) in about 15 g of tetrahydrofuran, using polystyrene as a standard substance. The GPC measurement can be performed under the following conditions. Measurement equipment: Waters2695 Column temperature: 40℃ Detector: RI2414 (differential refractometer) Carrier eluent flow rate: 0.3 ml / min (solvent: tetrahydrofuran) Columns: TSKgel SuperHZM-M (6.0 mm I.D. x 15 cm) and TSKgel SuperHZM-N (6.0 mm I.D. x 15 cm) in series (both manufactured by Tosoh Corporation).

[0069] The method for producing the vinyl copolymer (B) is not particularly limited, but from the viewpoint of the moldability of the final resin composition obtained and the color tone of the molded product, a continuous bulk polymerization method or a continuous solution polymerization method is preferably used. Here, the continuous bulk polymerization method is a method in which a monomer mixture is continuously charged over time and the bulk-polymerized vinyl copolymer is continuously discharged over time, and the continuous solution polymerization method is a method in which a monomer mixture and a solvent are continuously charged over time and the solution consisting of the solution-polymerized vinyl copolymer and the solvent is continuously discharged over time.

[0070] Any method can be employed for producing the vinyl copolymer (B) by continuous bulk polymerization or continuous solution polymerization, and an example thereof includes a method in which a vinyl monomer mixture (b) is polymerized in a polymerization tank and then the monomers are removed (removed from the solvent and devolatilized).

[0071] The polymerization vessel may be, for example, a mixing-type polymerization vessel having stirring blades such as paddle blades, turbine blades, propeller blades, blue margin blades, multistage blades, anchor blades, max blend blades, or double helical blades, or various tower-type reactors. Also usable as the polymerization reactor are multi-tube reactors, kneader-type reactors, and twin-screw extruders (see, for example, Assessment of Polymer Manufacturing Processes 10, "Assessment of Impact-Resistant Polystyrene," Society of Polymer Science, January 26, 1989).

[0072] When producing the vinyl copolymer (B), two or more of the above-mentioned polymerization tanks or polymerization reactors may be used, or two or more types of polymerization tanks or polymerization reactors may be combined as necessary. From the viewpoint of reducing the dispersity of the vinyl copolymer (B), it is preferable that the number of polymerization tanks or polymerization reactors is two or less, and a single-tank complete mixing type polymerization tank is more preferable.

[0073] The reaction mixture obtained by polymerization in the above-mentioned polymerization tank or polymerization reactor is usually then subjected to a demonomerization step to remove the monomer, solvent, and other volatile components. Examples of methods for demonomerization include a method in which volatile components are removed through a vent hole in a vented single- or twin-screw extruder under heating at normal or reduced pressure, a method in which volatile components are removed using an evaporator having a plate-fin heater such as a centrifugal type built into a drum, a method in which volatile components are removed using a thin-film evaporator such as a centrifugal type, and a method in which volatile components are removed by preheating and foaming using a multi-tube heat exchanger and flashing into a vacuum chamber. Among the methods for demonomerization, a method in which volatile components are removed using a vented single- or twin-screw extruder is particularly preferred.

[0074] When producing the vinyl copolymer (B), an initiator or a chain transfer agent may be used as appropriate. Examples of the initiator and chain transfer agent include the same initiators and chain transfer agents as those exemplified in the production method of the graft copolymer (A).

[0075] There is no particular limitation on the amount of initiator added to produce the vinyl copolymer (B). However, from the viewpoint of easily adjusting the weight average molecular weight of the vinyl copolymer (B) to the above-mentioned range, the amount is preferably 0.01 to 0.03 parts by mass per 100 parts by mass of the vinyl monomer mixture (b).

[0076] The amount of the chain transfer agent used to produce the vinyl copolymer (B) is not particularly limited, but from the viewpoint of easily adjusting the weight average molecular weight of the vinyl copolymer (B) to the above-mentioned range, it is preferably 0.05 parts by mass or more and 0.40 parts by mass or less per 100 parts by mass of the vinyl monomer mixture (b).

[0077] When the vinyl copolymer (B) is produced by a continuous bulk polymerization method or a continuous solution polymerization method, the polymerization temperature is not particularly limited, but is preferably 120°C or higher and 140°C or lower from the viewpoint of easily adjusting the weight average molecular weight of the vinyl copolymer (B) to the above-mentioned range.

[0078] When the vinyl copolymer (B) is produced by a continuous solution polymerization method, the amount of the solvent in the polymerization solution is preferably 30% by mass or less, more preferably 20% by mass or less, from the viewpoint of productivity. As the solvent, ethylbenzene or methyl ethyl ketone is preferred, and ethylbenzene is particularly preferred, from the viewpoint of polymerization stability.

[0079] The resin composition of the present invention is preferably formed by blending 10 to 60 parts by mass of graft copolymer (A) and 40 to 90 parts by mass of vinyl copolymer (B) per 100 parts by mass of the total of graft copolymer (A) and vinyl copolymer (B). By using 10 parts by mass or more of graft copolymer (A) and 90 parts by mass or less of vinyl copolymer (B), a decrease in impact resistance of the molded article can be suppressed. It is more preferable to use 20 parts by mass or more of graft copolymer (A) and 80 parts by mass or less of vinyl copolymer (B) per 100 parts by mass of the total of graft copolymer (A) and vinyl copolymer (B). Furthermore, by using 60 parts by mass or less of graft copolymer (A) and 40 parts by mass or more of vinyl copolymer (B), an increase in the melt viscosity of the final resin composition can be suppressed, while a decrease in fluidity, volatility, appearance, and color development can also be suppressed. It is more preferable to blend 50 parts by mass or less of the graft copolymer (A) and 50 parts by mass or more of the vinyl copolymer (B) per 100 parts by mass of the total of the graft copolymer (A) and the vinyl copolymer (B). The graft copolymer (A) may be a graft copolymer (A) containing two or more different rubber polymers (r). Furthermore, two or more types of the vinyl copolymer (B) may also be blended.

[0080] Component 3: Phosphate ester compound (E1) and polyoxyethylene alkylamine (E2) The resin composition according to the present invention contains either or both of a phosphoric acid ester compound (E1) represented by the following chemical formula (1) and a polyoxyethylene alkylamine (E2) represented by the following chemical formula (2).

[0081] The phosphate ester compound (E1) is represented by the following chemical formula (1).

[0082] [ka]

[0083] (R is an alkyl or alkenyl group having 8 to 22 carbon atoms, AO is an oxyalkylene group having 2 or 3 carbon atoms, n is an integer of 1 to 20, m is an integer of 1 or 2, M is a hydrogen atom, a Group 1 metal atom or a second metal atom, and q is 1 when M is a hydrogen atom or a Group 1 metal atom, or 1 / 2 when M is a second metal atom.) R in chemical formula (1) represents an alkyl group or alkenyl group having 8 to 22 carbon atoms. The alkyl group may be linear or branched, and may contain a ring structure such as a cycloalkyl structure. The number of carbon atoms in the alkyl group is preferably 12 or more, and more preferably 16 or less. Specifically, R is preferably an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, or an isotridecyl group.

[0084] AO represents an oxyalkylene group having 2 or 3 carbon atoms. The oxyalkylene group may be linear or branched. Specific examples include an oxyethylene group and an oxypropylene group.

[0085] M represents a hydrogen atom, a Group 1 metal atom, or a Group 2 metal atom, and examples of Group 1 metal atoms include sodium, potassium, lithium, rubidium, cesium, etc., and examples of Group 2 metal atoms include calcium, barium, magnesium, strontium, etc. Among these, M is preferably a hydrogen atom, sodium, potassium, calcium, or magnesium.

[0086] n is an integer of 1 to 20, preferably an integer of 3 or greater, and preferably an integer of 10 or less. When m is 2 or greater, AO may have a plurality of different groups. Specifically, AO may have both an oxyethylene group and an oxypropylene group.

[0087] Examples of the phosphate ester compound (E1) represented by chemical formula (1) include mono-n-dodecyltetraoxyethylene phosphate, di-n-dodecyltetraoxyethylene phosphate, mono-n-tridecyltetraoxyethylene phosphate, di-n-tridecyltetraoxyethylene phosphate, mono-n-tetradecyloxytetraoxyethylene phosphate, di-n-tetradecyloxytetraoxyethylene phosphate, mono-n-hexadecyloxytetraoxyethylene phosphate, di-n-hexadecyloxytetraoxyethylene phosphate, mono-n-octadecyloxytetraoxyethylene phosphate, Decyloxytetraoxyethylene phosphate, di-n-octadecyloxytetraoxyethylene phosphate, mono-n-decyloxypentaoxyethylene phosphate, di-n-decyloxypentaoxyethylene phosphate, mono-n-dodecyloxypentaoxyethylene phosphate, di-n-dodecyloxypentaoxyethylene phosphate, mono-n-tridecyloxypentaoxyethylene phosphate, di-n-tridecyloxypentaoxyethylene phosphate, mono-n-tetradecyloxypentaoxyethylene phosphate, di-n-tetradecyloxypenta Oxyethylene phosphate, mono-n-hexadecyloxypentaoxyethylene phosphate, di-n-hexadecyloxypentaoxyethylene phosphate, mono-n-octadecyloxypentaoxyethylene phosphate, di-n-octadecyloxypentaoxyethylene phosphate, mono-n-decyloxyhexaoxyethylene phosphate, di-n-decyloxyhexaoxyethylene phosphate, mono-n-dodecyloxyhexaoxyethylene phosphate, di-n-dodecyloxyhexaoxyethylene phosphate, mono-n-tridecyloxyhexaoxyethylene Phosphoric acid, di-n-tridecyloxyhexaoxyethylene phosphoric acid, mono-n-tetradecyloxyhexaoxyethylene phosphoric acid, di-n-tetradecyloxyhexaoxyethylene phosphoric acid, mono-n-hexadecyloxyhexaoxyethylene phosphoric acid, di-n-hexadecyloxyhexaoxyethylene phosphoric acid, mono-n-octadecyloxyhexaoxyethylene phosphoric acid, di-n-octadecyloxyhexaoxyethylene phosphoric acid, mono-n-decyloxyoctaoxyethylene phosphoric acid, di-n-decyloxyoctaoxyethylene phosphoric acid,Mono-n-dodecyloxyoctaoxyethylene phosphate, di-n-dodecyloxyoctaoxyethylene phosphate, mono-n-tridecyloxyoctaoxyethylene phosphate, di-n-tridecyloxyoctaoxyethylene phosphate, mono-n-tetradecyloxyoctaoxyethylene phosphate, di-n-tetradecyloxyoctaoxyethylene phosphate, mono-n-hexadecyloxyoctaoxyethylene phosphate, di-n-hexadecyloxyoctaoxyethylene phosphate, mono-n-octadecyloxyoctaoxyethylene phosphate, di- Linear alkyloxypolyoxyethylene phosphates such as n-octadecyloxyoctaoxyethylene phosphate, or their salts with Group 1 metals (alkali metals such as Na and K) or their salts with Group 2 metals (alkaline earth metals such as Ca and Mg), mono-n-isodecyloxytetraoxyethylene phosphate, di-n-isodecyloxytetraoxyethylene phosphate, mono-n-isododecyloxytetraoxyethylene phosphate, di-n-isododecyloxytetraoxyethylene phosphate, mono-n-isotridecyloxytetraoxyethylene phosphate Acid, di-n-isotridecyloxytetraoxyethylene phosphate, mono-n-isotetradecyloxytetraoxyethylene phosphate, di-n-isotetradecyloxytetraoxyethylene phosphate, mono-n-isohexadecyloxytetraoxyethylene phosphate, di-n-isohexadecyloxytetraoxyethylene phosphate, mono-n-isooctadecyloxytetraoxyethylene phosphate, di-n-isooctadecyloxytetraoxyethylene phosphate, mono-n-isodecyloxyhexaoxyethylene phosphate, di-n-isodecyloxy Dihexaoxyethylene phosphate, mono-n-isododecyloxyhexaoxyethylene phosphate, di-n-isododecyloxyhexaoxyethylene phosphate, mono-n-isotridecyloxyhexaoxyethylene phosphate, di-n-isotridecyloxyhexaoxyethylene phosphate, mono-n-isotetradecyloxyhexaoxyethylene phosphate, di-n-isotetradecyloxyhexaoxyethylene phosphate, mono-n-isohexadecyloxyhexaoxyethylene phosphate, di-n-isohexadecyloxyhexaoxyethylene phosphate,Mono-n-isooctadecyloxyhexaoxyethylene phosphate, di-n-isooctadecyloxyhexaoxyethylene phosphate, mono-n-isodecyloxyoctaoxyethylene phosphate, di-n-isodecyloxyoctaoxyethylene phosphate, mono-n-isododecyloxyoctaoxyethylene phosphate, di-n-isododecyloxyoctaoxyethylene phosphate, mono-n-isotridecyloxyoctaoxyethylene phosphate, di-n-isotridecyloxyoctaoxyethylene phosphate, mono-n-isotetradecyloxyoctaoxyethylene phosphate Examples of suitable phosphates include branched alkyloxypolyoxyethylene phosphates such as di-n-isotetradecyloxyoctaoxyethylene phosphate, mono-n-isohexadecyloxyoctaoxyethylene phosphate, di-n-isohexadecyloxyoctaoxyethylene phosphate, mono-n-isooctadecyloxyoctaoxyethylene phosphate, and di-n-isooctadecyloxyoctaoxyethylene phosphate, or their Group 1 metal (alkali metal, e.g., Na, K) salts or their Group 2 metal (alkaline earth metal, e.g., Ca, Mg) salts, but are not limited to these. Among these, from the viewpoint of improving the appearance and color development of molded articles, preferred are mono-n-dodecyloxytetraoxyethylene phosphate, mono-n-isododecyloxytetraoxyethylene phosphate, mono-n-tridecyloxyhexaoxyethylene phosphate, mono-n-isotridecyloxyhexaoxyethylene phosphate, or their Group 1 metal (alkali metal, e.g., Na, K) salts or their Group 2 metal (alkaline earth metal, e.g., Ca, Mg) salts.

[0088] Other examples of the phosphate ester compound represented by chemical formula (1) include mono-n-dodecyltetraoxypropylene phosphate, di-n-dodecyltetraoxypropylene phosphate, mono-n-tridecyltetraoxypropylene phosphate, di-n-tridecyltetraoxypropylene phosphate, mono-n-tetradecyloxytetraoxypropylene phosphate, di-n-tetradecyloxytetraoxypropylene phosphate, mono-n-hexadecyloxytetraoxypropylene phosphate, di-n-hexadecyloxytetraoxypropylene phosphate, mono-n -Octadecyloxytetraoxypropylene phosphate, di-n-octadecyloxytetraoxypropylene phosphate, mono-n-decyloxypentaoxypropylene phosphate, di-n-decyloxypentaoxypropylene phosphate, mono-n-dodecyloxypentaoxypropylene phosphate, di-n-dodecyloxypentaoxypropylene phosphate, mono-n-tridecyloxypentaoxypropylene phosphate, di-n-tridecyloxypentaoxypropylene phosphate, mono-n-tetradecyloxypentaoxypropylene phosphate, di-n-tetradecyloxypentaoxypropylene phosphate Toradecyloxypentaoxypropylene phosphate, mono-n-hexadecyloxypentaoxypropylene phosphate, di-n-hexadecyloxypentaoxypropylene phosphate, mono-n-octadecyloxypentaoxypropylene phosphate, di-n-octadecyloxypentaoxypropylene phosphate, mono-n-decyloxyhexaoxypropylene phosphate, di-n-decyloxyhexaoxypropylene phosphate, mono-n-dodecyloxyhexaoxypropylene phosphate, di-n-dodecyloxyhexaoxypropylene phosphate, mono-n- Tridecyloxyhexaoxypropylene phosphate, di-n-tridecyloxyhexaoxypropylene phosphate, mono-n-tetradecyloxyhexaoxypropylene phosphate, di-n-tetradecyloxyhexaoxypropylene phosphate, mono-n-hexadecyloxyhexaoxypropylene phosphate, di-n-hexadecyloxyhexaoxypropylene phosphate, mono-n-octadecyloxyhexaoxypropylene phosphate, di-n-octadecyloxyhexaoxypropylene phosphate, mono-n-decyloxyoctadecyloxypropylene phosphate,Di-n-decyloxyoctaoxypropylene phosphate, mono-n-dodecyloxyoctaoxypropylene phosphate, di-n-dodecyloxyoctaoxypropylene phosphate, mono-n-tridecyloxyoctaoxypropylene phosphate, di-n-tridecyloxyoctaoxypropylene phosphate, mono-n-tetradecyloxyoctaoxypropylene phosphate, di-n-tetradecyloxyoctaoxypropylene phosphate, mono-n-hexadecyloxyoctaoxypropylene phosphate, di-n-hexadecyloxyoctaoxypropylene linear alkyloxypolyoxyethylene phosphates such as mono-n-octadecyloxyoctaoxypropylene phosphate, di-n-octadecyloxyoctaoxypropylene phosphate, or their salts with Group 1 metals (alkali metals such as Na and K) or their salts with Group 2 metals (alkaline earth metals such as Ca and Mg); mono-n-isodecyloxytetraoxypropylene phosphate, di-n-isodecyloxytetraoxypropylene phosphate, mono-n-isododecyloxytetraoxypropylene phosphate, di-n-isododecyloxytetraoxypropylene phosphate, Tri-oxypropylene phosphate, mono-n-isotridecyloxytetraoxypropylene phosphate, di-n-isotridecyloxytetraoxypropylene phosphate, mono-n-isotetradecyloxytetraoxypropylene phosphate, di-n-isotetradecyloxytetraoxypropylene phosphate, mono-n-isohexadecyloxytetraoxypropylene phosphate, di-n-isohexadecyloxytetraoxypropylene phosphate, mono-n-isooctadecyloxytetraoxypropylene phosphate, di-n-isooctadecyloxytetraoxypropylene phosphate Oxypropylene phosphate, mono-n-isodecyloxyhexaoxypropylene phosphate, di-n-isodecyloxyhexaoxypropylene phosphate, mono-n-isododecyloxyhexaoxypropylene phosphate, di-n-isododecyloxyhexaoxypropylene phosphate, mono-n-isotridecyloxyhexaoxypropylene phosphate, di-n-isotridecyloxyhexaoxypropylene phosphate, mono-n-isotetradecyloxyhexaoxypropylene phosphate, di-n-isotetradecyloxyhexaoxypropylene phosphate,Mono-n-isohexadecyloxyhexaoxypropylene phosphate, di-n-isohexadecyloxyhexaoxypropylene phosphate, mono-n-isooctadecyloxyhexaoxypropylene phosphate, di-n-isooctadecyloxyhexaoxypropylene phosphate, mono-n-isodecyloxyoctaoxypropylene phosphate, di-n-isodecyloxyoctaoxypropylene phosphate, mono-n-isododecyloxyoctaoxypropylene phosphate, di-n-isododecyloxyoctaoxypropylene phosphate, mono-n-isotridecyloxyoctaoxypropylene phosphate, di-n-isotridecyloxyoctaoxypropylene phosphoric acid Examples of the alkyl ester include, but are not limited to, branched alkyloxypolyoxypropylene phosphates such as mono-n-isotetradecyloxyoctaoxypropylene phosphate, di-n-isotetradecyloxyoctaoxypropylene phosphate, mono-n-isohexadecyloxyoctaoxypropylene phosphate, di-n-isohexadecyloxyoctaoxypropylene phosphate, mono-n-isooctadecyloxyoctaoxypropylene phosphate, and di-n-isooctadecyloxyoctaoxypropylene phosphate, as well as salts of Group 1 metals (alkali metals such as Na and K) and salts of Group 2 metals (alkaline earth metals such as Ca and Mg). Among these, from the viewpoint of improving the appearance and color development of molded articles, mono-n-dodecyloxytetraoxypropylene phosphate, mono-n-isododecyloxytetraoxypropylene phosphate, mono-n-tridecyloxyhexaoxypropylene phosphate, mono-n-isotridecyloxyhexaoxypropylene phosphate, or their salts with Group 1 metals (alkali metals such as Na and K) or their salts with Group 2 metals (alkaline earth metals such as Ca and Mg) are preferably used.

[0089] These phosphate ester compounds (E1) may be used alone or in combination of two or more. When a mixture of two or more is used, it may be a mixture of a monoalkyl ester and a dialkyl ester, and in this case, the mixing ratio of the monoalkyl ester and the dialkyl ester is not particularly limited.

[0090] Examples of products containing the phosphate ester compound (E1) of chemical formula (1) include NC-718 manufactured by Sanyo Chemical Industries, Ltd., Phosphanol LS-529, Phosphanol RS-610, Phosphanol RD-510Y, Phosphanol RS-620, Phosphanol RS-630, Phosphanol RS-640, Phosphanol RS-650, Phosphanol RS-660, and Phosphanol RS-6103C manufactured by Toho Chemical Industry Co., Ltd., and Latemul P-0405, Latemul P-0406, and Latemul P-0407 manufactured by Kao Corporation.

[0091] The phosphate ester compound (E1) used in the present invention is preferably such that part of M in chemical formula (1) is a Group 2 metal atom. When part of M is a Group 2 metal atom, the appearance, color development, and tensile elongation of the molded article are further improved. Of these, calcium is preferably used.

[0092] When M is a Group 2 metal atom, two molecules of monovalent phosphate ester are paired with one divalent metal atom, so q is 1 / 2.

[0093] The content of Group 2 metal atoms in 100% by mass of the phosphate ester compound (E1) used in the present invention is more preferably 2% by mass or more and 5% by mass or less. When the content of Group 2 metal atoms in 100% by mass of the phosphate ester compound (E1) is 2% or more, the appearance, color development, and tensile elongation of a molded article can be further improved. On the other hand, when the content of Group 2 metal atoms in 100% by mass of the phosphate ester compound (E1) exceeds 5% by mass, the viscosity of an aqueous solution containing the phosphate ester compound (E1) increases. This leads to poor solubility of the phosphate ester compound (E1) in the emulsion-polymerized latex described below, which may further deteriorate the emulsion stability of the latex.

[0094] In addition, an aqueous solution of the phosphate ester compound (E1) in which the content of the Group 2 metal atom in 100% by mass of the phosphate ester compound (E1) is 2% by mass or more and 5% by mass or less can be easily produced by adding a prescribed amount of a hydroxide of a Group 2 metal atom, specifically calcium hydroxide or the like, to a product containing the phosphate ester compound (E1) and stirring at 60 °C for about 30 minutes.

[0095] The polyoxyethylene alkylamine (E2) is represented by the following chemical formula (2).

[0096]

Chemical formula

[0097] (In Chemical formula (2), R represents an alkyl group or an alkenyl group having 8 to 22 carbon atoms, and m + n is a positive integer satisfying the relationship of 2 < m + n ≤ 20.) Examples of the polyoxyethylene alkylamine (E2) represented by Chemical formula (2) include N,N-dipolyoxyethylene-N-laurylamine (3), N,N-dipolyoxyethylene-N-laurylamine (10), N,N-dipolyoxyethylene-N-myristylamine (4), N,N-dipolyoxyethylene-N-myristylamine (6), N,N-dipolyoxyethylene-N-palmitoylamine (5), N,N-dipolyoxyethylene-N-stearylamine (9), N,N-dipolyoxyethylene-N-oleylamine (8), N,N-dipolyoxyethylene-N-behenylamine (3), etc., but are not limited thereto. These polyoxyethylene alkylamines (E2) may be used alone or in combination of two or more. The numbers in parentheses indicate the sum of m + n.

[0098] Polyoxyethylene alkylamine (E2) represented by chemical formula (2) is obtained by an addition reaction between an aliphatic amine having 8 to 22 carbon atoms and ethylene oxide, or by a dehydration reaction between an aliphatic amine and polyoxyethylene. The fatty acid amine is generally a saturated aliphatic amine having 8 to 22 carbon atoms, such as laurylamine, myristylamine, or stearylamine, used alone, or a mixture containing these saturated amines and unsaturated aliphatic amines, such as oleylamine (for example, higher aliphatic amines made from coconut oil, beef tallow, or the like).

[0099] Examples of products containing polyoxyethylene alkylamine (E2) of chemical formula (2) include Nymeen L-202, Nymeen L-207, Nymeen F-202, Nymeen F-215, Nymeen T2-210, Nymeen T2-230, Nymeen S-210, Nymeen S-215, Nymeen S-220, and Nymeen O-205, all of which are manufactured by NOF Corporation; Anstex SA-35B, manufactured by Toho Chemical Industry Co., Ltd.; and SN Wet S, manufactured by San Nopco Ltd.

[0100] The resin composition of the present invention contains either or both of a phosphate ester compound (E1) and a polyoxyethylene alkylamine (E2), and the ratio of the total amount of the phosphate ester compound (E1) and the polyoxyethylene alkylamine (E2) to the total amount of the entire resin composition is 60 ppm (mass / mass) or more. This ratio is preferably 120 ppm (mass / mass) or more, more preferably 300 ppm (mass / mass) or more. The upper limit is preferably 600 ppm (mass / mass). If the total amount of the phosphate ester compound (E1) and the polyoxyethylene alkylamine (E2) to the total amount of the entire resin composition is less than 60 ppm (mass / mass), the tensile elongation, appearance, and color development of the molded article will be reduced. On the other hand, if this ratio exceeds 600 ppm (mass / mass), volatility may be significantly reduced, which is undesirable.

[0101] For reasons that will be described later, the phosphate ester compound (E1) and the polyoxyethylene alkylamine (E2) are preferably added to an emulsified latex of the graft copolymer (A) obtained by graft copolymerization.

[0102] The total amount of either or both of the phosphate ester compound (E1) and the polyoxyethylene alkylamine (E2) added is preferably 0.04 to 0.4 parts by mass relative to 100 parts by mass of the graft copolymer (A). More preferably, it is 0.04 to 0.2 parts by mass. When the total amount of either or both of the phosphate ester compound (E1) and the polyoxyethylene alkylamine (E2) is 0.04 parts by mass or more relative to 100 parts by mass of the graft copolymer (A), the tensile elongation, appearance, and color development of the molded article can be improved. On the other hand, when the total amount is 0.4 parts by mass or less, a significant deterioration in the emulsion latex state of the graft copolymer (A) can be suppressed.

[0103] Component 4: A heat-resistant vinyl copolymer (C) obtained by copolymerizing a vinyl monomer mixture (c) containing at least an aromatic vinyl monomer (c1) and a maleimide monomer (c2). The resin composition of the present invention may optionally contain a heat-resistant vinyl copolymer (C) obtained by copolymerizing a vinyl monomer mixture (c) containing at least an aromatic vinyl monomer (c1) and a maleimide monomer (c2). The inclusion of the heat-resistant vinyl copolymer (C) can impart heat resistance to the final resin composition.

[0104] Examples of the aromatic vinyl monomer (c1) in the vinyl monomer mixture (c) include those exemplified as the aromatic vinyl monomer (a1), with styrene being preferred.

[0105] Examples of the maleimide monomer (c2) in the vinyl monomer mixture (c) include N-methylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-dodecylmaleimide, N-cyclohexylmaleimide, and N-phenylmaleimide. Two or more of these may be contained as the maleimide monomer (c2). Among the maleimide monomers (c2), N-phenylmaleimide is preferred from the viewpoint of improving the heat resistance of the final resin composition.

[0106] Furthermore, there are no particular limitations on the vinyl monomer other than the aromatic vinyl monomer (c1) and maleimide monomer (c2) described above, as long as it does not impair the effects of the present invention. Specific examples of other monomers include vinyl cyanide monomer (c3), unsaturated fatty acid, and acrylamide monomer, and two or more of these may be contained.

[0107] Examples of the vinyl cyanide monomer (c3) in the vinyl monomer mixture (c) include those exemplified as the vinyl cyanide monomer (a2), and acrylonitrile is preferred.

[0108] The composition ratio of each monomer used in the heat-resistant vinyl copolymer (C) is not particularly limited, but is preferably 36 to 65 mass% aromatic vinyl monomer (c1), 35 to 52 mass% maleimide monomer (c2), preferably 37 to 50 mass% vinyl cyanide monomer (c3), and 0 to 12 mass% vinyl cyanide monomer (c3). In particular, if the content of maleimide monomer (c2) is less than 35 mass%, the effect of improving the heat resistance of the final resin composition is small, while if it exceeds 52 mass%, the moldability of the final resin composition may be impaired.

[0109] The reduced viscosity of the heat-resistant vinyl copolymer (C) measured with an Ubbelohde viscometer in a 0.4 g / dL dimethyl sulfoxide solution at 30°C is preferably 0.3 to 0.7 dL / g, more preferably 0.4 to 0.6 dL / g. If the reduced viscosity of the heat-resistant vinyl copolymer (C) is less than 0.3 dL / g, the impact resistance of the molded article may decrease, while if it exceeds 0.7 dL / g, the fluidity of the final resin composition may decrease, resulting in poor moldability.

[0110] The content of the heat-resistant vinyl copolymer (C) in the resin composition of the present invention is preferably 10 to 38 mass%, more preferably 12 to 36 mass%, and even more preferably 15 to 35 mass%, based on 100 mass% of the total amount of all resin components. By setting the content within this range, the effect of improving the heat resistance of the molded article is further enhanced, and the impact resistance of the molded article and the flowability of the final resin composition are also more significantly improved.

[0111] In the case where a heat-resistant vinyl copolymer (C) is used, the phosphate ester compound (E1) has a long-chain alkyl or alkenyl group (hydrophobic part), a polyoxyalkylene group (hydrophilic part), and a phosphate ester group (polar part) in its molecular structure, and the polyoxyethylene alkylamine (E2) has three parts in its molecular structure: a long-chain alkyl or alkenyl group (hydrophobic part), a polyoxyalkylene group (hydrophilic part), and a tertiary amino group (polar part).The hydrophobic part has an affinity for the rubber polymer (r) in the graft copolymer (A), while the hydrophilic part and polar part have an affinity for the nitrile or imide groups of the vinyl copolymer (B) or the highly polar heat-resistant vinyl copolymer (C).As a result, the phosphate ester compound (E1) and the polyoxyethylene alkylamine (E2) act as compatibilizers. The phosphate ester compound (E1) and polyoxyethylene alkylamine (E2) are thought to inhibit aggregation of the rubbery polymer (r) in the graft copolymer (A), thereby achieving high appearance and color development. In particular, when combining an acrylic rubber, which tends to have a relatively small number of double bonds and a low graft ratio, with a highly polar heat-resistant vinyl copolymer (C), aggregation of the acrylic rubber in the graft copolymer (A) is more likely to occur. However, the inclusion of either or both of the phosphate ester compound (E1) and polyoxyethylene alkylamine (E2) can inhibit aggregation of the acrylic rubber in the graft copolymer (A). Furthermore, the effects of the phosphate ester compound (E1) and polyoxyethylene alkylamine (E2) are particularly pronounced when a heat-resistant vinyl copolymer (C) is used.

[0112] In order to more effectively exert the above-mentioned effects, it is preferred that the phosphate ester compound (E1) and the polyoxyethylene alkylamine (E2) are blended in the emulsified latex of the graft copolymer (A) and are present around the graft copolymer (A).

[0113] The resin composition of the present invention may contain, within the scope of the object of the present invention, inorganic fillers such as glass fiber, glass powder, glass beads, glass flakes, alumina, alumina fiber, carbon fiber, graphite fiber, stainless steel fiber, whisker, potassium titanate fiber, wollastonite, asbestos, hard clay, calcined clay, talc, kaolin, mica, calcium carbonate, magnesium carbonate, aluminum oxide, and minerals; impact modifiers such as silicone compounds; antioxidants such as hindered phenols, sulfur-containing compounds, and phosphorus-containing organic compounds; heat stabilizers such as phenols and acrylates; benzotriazoles, benzophenones, and the like. Other compounds that may be compounded include ultraviolet absorbers such as phenols or salicylates; hindered amine light stabilizers; lubricants and plasticizers such as higher fatty acids, acid esters, acid amides or higher alcohols; release agents such as montanic acid and its salts, its esters, its half esters, stearyl alcohol, stearamide and ethylene wax; various flame retardants; flame retardant assistants; color inhibitors such as phosphites and hypophosphites; neutralizing agents such as phosphoric acid, monosodium phosphate, maleic anhydride and succinic anhydride; nucleating agents; antistatic agents such as amines, sulfonic acids and polyethers; colorants such as carbon black, pigments and dyes; and bluing agents.

[0114] Next, a method for producing the resin composition of the present invention will be described. The resin composition of the present invention can be produced, for example, by the following steps: graft copolymerizing a monomer mixture (a) containing at least an aromatic vinyl monomer (a1) and a vinyl cyanide monomer (a2) in the presence of a rubber polymer (r) to obtain an emulsion-polymerized latex; adding either or both of a phosphate ester compound (E1) and a polyoxyethylene alkylamine (E2) to the emulsion-polymerized latex; and then contacting the emulsion-polymerized latex with an aqueous sulfuric acid solution to obtain a graft copolymer (A) (Step A). a step (step B) of obtaining a vinyl copolymer (B) obtained by copolymerizing a monomer mixture (b) containing at least an aromatic vinyl monomer (b1) and a vinyl cyanide monomer (b2); a step (step C) of obtaining a heat-resistant vinyl copolymer (C) obtained by copolymerizing a vinyl monomer mixture (c) containing at least an aromatic vinyl monomer (c1) and a maleimide monomer (c2) as necessary; The graft copolymer (A), vinyl copolymer (B), and heat-resistant vinyl copolymer (C) obtained in steps A, B, and C are mixed together (the heat-resistant vinyl copolymer (C) is an optional component). The melt-kneading method is not particularly limited, but methods using a single- or twin-screw in a cylinder equipped with a heating device and a vent are possible. The heating temperature during melt-kneading is typically selected from the range of 210 to 320°C, but the temperature gradient during melt-kneading can also be freely set within a range that does not impair the objectives of the present invention. When twin screws are used, they may rotate in the same or opposite directions.

[0115] The resin composition of the present invention can be molded by any molding method. Examples of molding methods include injection molding, extrusion molding, inflation molding, blow molding, vacuum molding, compression molding, and gas-assisted molding, with injection molding being preferred. The cylinder temperature during injection molding is preferably 210°C or higher and 320°C or lower, and the mold temperature is preferably 30°C or higher and 80°C or lower.

[0116] The resin composition of the present invention can be widely used as a molded article of any shape, such as a film, sheet, fiber, cloth, nonwoven fabric, injection molded article, extrusion molded article, vacuum / compression molded article, blow molded article, or composite with other materials.

[0117] The resin composition of the present invention has excellent appearance (fisheyes, gloss), color development, impact resistance, and tensile elongation, all of which are caused by the aggregation of rubber polymers, and is therefore useful for applications such as home appliances, communication-related equipment, general merchandise, and automotive materials. The heat-resistant vinyl copolymer-containing resin composition to which heat resistance has been imparted combines fluidity and impact resistance suitable for large molded products, and the molded products have excellent appearance, making it particularly suitable for use in automotive exteriors such as rear spoilers, wheel caps, door mirrors, radiator grilles, and lamp housings, and automotive interiors such as power window panels, center consoles, center clusters, lever controllers, and console boxes. [Example]

[0118] EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention should not be construed as being limited to these examples. First, the evaluation methods will be described.

[0119] (1) Volume average particle size of rubber polymer After diluting and dispersing the latex of rubber polymer (r) in an aqueous medium, the particle size distribution was measured using a laser scattering diffraction particle size distribution analyzer "LS 13 320XR" (Beckman Coulter, Inc.). From the particle size distribution, the volume average particle size of rubber polymer (r) was calculated.

[0120] (2) Graft ratio of graft copolymer (A) Approximately 1 g of graft copolymer (A) is added to 80 ml of solvent and refluxed in a 70°C water bath for 3 hours. This solution is centrifuged at 8,000 rpm (10,000 G) for 40 minutes, and the insoluble matter is filtered to obtain a solvent-insoluble fraction. The resulting solvent-insoluble fraction is dried under reduced pressure at 80°C for 5 hours, and its mass (referred to as n in the formula below) is measured, and the graft ratio is calculated using the formula below. Here, m is the sample mass of graft copolymer (A) used, and X is the rubber polymer content (mass%) of graft copolymer (A). Grafting rate (%) = {[(n) - ((m) × X / 100)] / [(m) × X / 100]} × 100.

[0121] When the rubber polymer (r) was polybutadiene, acetone was used as the solvent, and when it was acrylic rubber, acetonitrile was used as the solvent.

[0122] (3) Contents of phosphoric acid ester compound (E1) and polyoxyethylene alkylamine (E2) in the resin composition 10 mL of chloroform was added to 0.1 g of the resin composition and allowed to stand for 12 hours. After ultrasonic treatment for 1 hour, 0.1 mL of the prepared solution was collected in a microtube. 0.9 mL of 1% by volume formic acid in methanol was added to the prepared solution to dilute it 10-fold and vigorously stirred. The mixture was then centrifuged (15,000 G) for 15 minutes, and the supernatant was used as the sample solution.

[0123] LC / MS analysis was performed under the following conditions, selecting three monitor ions, and measuring the contents of the phosphate ester compound (E1) and polyoxyethylene alkylamine (E2) in the resin composition for each monitor ion using the calibration curves of the respective standard solutions prepared in advance, and calculating the number average values. Measurement conditions for phosphate ester compounds (E1): HPLC: LC-20 [Shimadzu Corporation] Mass spectrometer: API5000 [manufactured by SCIEX] Column: ODS column Mobile phase: A. 10 mmol / L ammonium acetate aqueous solution B. Acetonitrile Gradient conditions Injection volume: 3μL Ionization: APCI Detection: Negative ion detection Measurement mode: SRM (Selected reaction monitoring) Monitor ions: Tridecyloxypentaoxyethylene phosphate * (Q1 m / z 499.5, Q3 m / z 79.0) Tridecyloxyhexaoxyethylene phosphate *(Q1 m / z 543.5, Q3 m / z 79.0) Tridecyloxyheptaoxyethylene phosphate * (Q1 m / z 587.5, Q3 m / z 79.0) *[MH] - Set as monitor ion Measurement conditions for polyoxyethylene alkylamine (E2): HPLC: LC-20 [Shimadzu Corporation] Mass spectrometer: API5000 [manufactured by SCIEX] Column: ODS column Mobile phase: A. 10 mmol / L ammonium acetate aqueous solution B. Acetonitrile Gradient conditions Injection volume: 2μL Ionization: APCI Detection: Positive ion detection Measurement mode: SRM (Selected reaction monitoring) Monitor ions: N,N-dipolyoxyethylene-N-laurylamine (4.5) * (Q1 m / z 582.5, Q3 m / z 344.4) N,N-dipolyoxyethylene-N-laurylamine (5.5) * (Q1 m / z 626.6, Q3 m / z 344.4) N,N-dipolyoxyethylene-N-laurylamine (5.6) * (Q1 m / z 626.6, Q3 m / z 344.4) *[M+H] + Set as monitor ion The numbers in parentheses indicate the values ​​of m and n in chemical formula (2).

[0124] (4) Amount of aggregates 100g of emulsified latex (solids equivalent) of a graft copolymer with a rubber polymer core was placed in a 500L beaker and stirred for 15 minutes at 500 rpm using a stirrer. The latex was then filtered using a 100-mesh wire screen, washed with water, and the aggregates collected on the screen were dried in a dryer at 150°C for 15 minutes, and the mass after drying was calculated. Note that A represents the best result. Mass of aggregates less than 0.5g: A Mass of aggregates is 0.5g or more but less than 1.5g: B Mass of aggregates is 1.5g or more: C (5) Impact resistance evaluation (Charpy impact strength) The resin composition pellets used as samples were dried in a hot air dryer at 80°C for 3 hours, and then loaded into an SE-50DU molding machine manufactured by Sumitomo Heavy Industries, Ltd. with a cylinder temperature set to 230°C, and 4 mm thick dumbbell test pieces were molded at a mold temperature of 60°C and a molding cycle of 30 seconds. Charpy impact strength was measured for five of the resulting dumbbell test pieces using a method in accordance with ISO179, and the number average value was calculated.

[0125] (6) Tensile elongation evaluation (tensile elongation) The resin composition pellets used as samples were dried in a hot air dryer at 80°C for 3 hours, and then loaded into an SE-50DU molding machine manufactured by Sumitomo Heavy Industries, Ltd. with a cylinder temperature set to 230°C, and molded into 4 mm thick dumbbell test pieces at a mold temperature of 60°C and a molding cycle of 30 seconds. Tensile elongation was measured for each of five obtained dumbbell test pieces using a method in accordance with ISO 527, and the number average value was calculated.

[0126] (7) Appearance evaluation (glossiness) The resin composition pellets used as samples were dried in a hot air dryer at 80°C for 3 hours, then loaded into an SE-50DU molding machine manufactured by Sumitomo Heavy Industries, Ltd. with a cylinder temperature set to 250°C, and molded into rectangular plate molded products (length 90 mm, width 50 mm, thickness 2.5 mm) at an injection speed of 50 mm / s, a mold temperature of 60°C, and a molding cycle of 20 seconds. The gloss at 20° was measured for five of the obtained rectangular plate molded products in accordance with JIS Z8741 (established in 1997), and the number average value was calculated.

[0127] (8) Color development evaluation (L value) The resin composition pellets used as samples were dried in a hot air dryer at 80°C for 3 hours, then loaded into an SE-50DU molding machine manufactured by Sumitomo Heavy Industries, Ltd., with a cylinder temperature set to 250°C, and molded into rectangular plate molded products (length 90 mm, width 50 mm, thickness 2.5 mm) at an injection speed of 50 mm / s, a mold temperature of 60°C, and a molding cycle of 20 seconds. The L value of five of the obtained rectangular plate molded products was measured in accordance with JIS K7103 (established in 1971), and the number average value was calculated.

[0128] (9) Volatility evaluation (mold contamination) The resin composition pellets used as samples were dried in a hot air dryer at 80°C for 3 hours, then loaded into a PS-60E molding machine manufactured by Nissei Plastic Industrial Co., Ltd. with a cylinder temperature set to 280°C. 1,000 injection moldings were performed on rectangular molded products (100 mm long, 120 mm wide, 3 mm thick) at a mold temperature of 60°C and a molding cycle of 30 seconds. The mold contamination was evaluated using the following criteria, with A representing the best result. No change observed on the mold surface: A Cloudiness is observed on the mold surface: B The mold surface is dirty and the appearance of the molded product is poor: C (10) Heat resistance evaluation The resin composition pellets used as samples were dried in a hot air dryer at 80°C for 3 hours, and then loaded into an SE-50DU molding machine manufactured by Sumitomo Heavy Industries, Ltd. with a cylinder temperature set to 230°C, and 4 mm thick dumbbell test pieces were molded at a mold temperature of 60°C and a molding cycle of 30 seconds. The heat distortion temperature of each of the obtained dumbbell test pieces, three of which were measured in accordance with ISO 75-2 (established in 2004, under a load of 1.8 MPa), and the number average value was calculated.

[0129] (11) Morphological evaluation The resin composition pellets obtained in Example 14 and Comparative Example 7 were dried for 3 hours in a hot air dryer at 80°C and then loaded into a SE-50DU molding machine manufactured by Sumitomo Heavy Industries, Ltd., with a cylinder temperature set to 230°C. A 4 mm-thick dumbbell test specimen was molded at a mold temperature of 60°C and a molding cycle of 30 seconds. The resulting dumbbell test specimens were stained with osmic acid and ruthenium, and the morphology of the specimens was observed at 5000x magnification using a Hitachi High-Technologies Corporation transmission electron microscope (TEM) HT7700 to evaluate the cohesion of the rubbery polymer. The white areas in the TEM images represent the acrylic rubbery polymer, and the black areas represent polybutadiene rubber. The gray areas represent components other than the rubbery polymer.

[0130] Phosphate ester compound (E1) and polyoxyethylene alkylamine (E2): Phosphate ester compounds (E1-1) A 30 L reactor equipped with a stirrer was charged with 100 parts by mass of Phosphanol RS-610 manufactured by Toho Chemical Industry Co., Ltd., and the temperature was raised to 60°C. 3 parts by mass of calcium hydroxide was added with stirring, and the reaction was carried out for 30 minutes to obtain a phosphate ester compound (E1-1). The content of Group 2 metal atoms in 100% by mass of the obtained phosphate ester compound (E1-1) was 1.6% by mass.

[0131] Phosphate ester compounds (E1-2) A phosphate compound (E1-2) was obtained in the same manner as the phosphate compound (E1-1) except for adding 6 parts by mass of calcium hydroxide. The content of Group 2 metal atoms in 100% by mass of the obtained phosphate compound (E1-2) was 3.2% by mass.

[0132] Polyoxyethylene alkylamine (E2-1) SN Wet S manufactured by San Nopco Ltd. was used.

[0133] Graft copolymer (A): (Production Example 1) Graft Copolymer (A-1) Containing Phosphate Ester Compound (E1-1) 20m with stirring blades 3 Into a reaction vessel, 50 parts by mass (solids content equivalent) of polybutadiene latex (volume average particle size of rubber: 0.24 μm), 130 parts by mass of pure water, 0.4 parts by mass of sodium laurate, 0.2 parts by mass of glucose, 0.2 parts by mass of sodium pyrophosphate, and 0.01 parts by mass of ferrous sulfate were charged, and after nitrogen substitution, the temperature was adjusted to 60°C, and a monomer mixture of 6.7 parts by mass of styrene, 2.5 parts by mass of acrylonitrile, and 0.058 parts by mass of t-dodecyl mercaptan was added over 30 minutes with stirring.

[0134] Next, an initiator mixture consisting of 0.32 parts by mass of cumene hydroperoxide, 1.5 parts by mass of the emulsifier sodium laurate, and 25 parts by mass of purified water was added dropwise over 5 hours. Simultaneously with this addition, a monomer mixture consisting of 29.8 parts by mass of styrene, 11.0 parts by mass of acrylonitrile, and 0.193 parts by mass of t-dodecyl mercaptan was added dropwise over 3.5 hours. After polymerization was completed, the resulting graft copolymer (A-1) latex was cooled to 40°C, and 0.5 parts by mass of the reaction product of p-cresol, dicyclopentadiene, and isobutylene and 0.2 parts by mass of phosphate ester compound (E1-1) were added while stirring. The mixture was then coagulated with 1.5% by mass sulfuric acid, neutralized with sodium hydroxide, washed, centrifuged, and dried to obtain phosphate ester compound (E1-1)-containing graft copolymer (A-1) (monomer ratio: 73% by mass styrene, 27% by mass acrylonitrile). The graft ratio of the resulting graft copolymer (A-1) was 43%.

[0135] (Production Example 2) Polyoxyethylene alkylamine (E2-1)-containing graft copolymer (A-2) Graft copolymer (A-2) containing phosphate ester compound (E2-1) was obtained in the same manner as in Production Example 1, except that SN Wet S (E2-1) manufactured by San Nopco Ltd. was used instead of phosphate ester compound (E1-1) and the amount added was changed to 0.3 parts by mass.

[0136] (Production Example 3) Graft copolymer (A-3) containing phosphoric acid ester compound (E1-1) 20m with stirring blades 3 A reaction vessel was charged with 150 parts by weight of pure water and 0.7 parts by weight (solids equivalent) of a 25% by weight disproportionated potassium rosinate aqueous solution (emulsifier). The system was then purged with nitrogen gas, and the temperature was raised to 62°C. A mixture of 14.9 parts by weight of n-butyl acrylate and 0.1 parts by weight of allyl methacrylate was added over 30 minutes with stirring. Next, 0.2 parts by weight (solids equivalent) of a 2% by weight aqueous potassium persulfate solution was continuously added over 285 minutes. After 105 minutes had elapsed since the start of the potassium persulfate aqueous solution addition, the internal temperature was raised to 65°C, and a mixture of 42.28 parts by weight of n-butyl acrylate and 0.22 parts by weight of allyl methacrylate was added over 75 minutes, followed by the addition of a mixture of 41.63 parts by weight of n-butyl acrylate and 0.87 parts by weight of allyl methacrylate over 75 minutes. Furthermore, 180 minutes after the start of the addition of the potassium persulfate aqueous solution, 1.3 parts by mass (solids equivalent) of a 25% by mass aqueous solution of disproportionated potassium rosinate was added over 105 minutes. After the addition of the potassium persulfate aqueous solution and the disproportionated potassium rosinate aqueous solution was completed, the internal temperature was raised to 70°C and maintained at that temperature for another hour, yielding an acrylic rubber latex with a polymerization rate of 95%.

[0137] 50 parts by mass (solids content equivalent) of acrylic rubber latex (volume average particle size of rubber: 0.13 μm), 130 parts by mass of pure water, 0.4 parts by mass of sodium laurate, 0.2 parts by mass of glucose, 0.2 parts by mass of sodium pyrophosphate, and 0.01 parts by mass of ferrous sulfate were charged, and after nitrogen substitution, the temperature was adjusted to 60°C. A monomer mixture of 6.7 parts by mass of styrene, 2.5 parts by mass of acrylonitrile, and 0.058 parts by mass of t-dodecyl mercaptan was added over 30 minutes with stirring.

[0138] Next, an initiator mixture of 0.32 parts by weight of cumene hydroperoxide, 1.5 parts by weight of the emulsifier sodium laurate, and 25 parts by weight of purified water was added dropwise over 5 hours. Simultaneously with this addition, a monomer mixture of 29.8 parts by weight of styrene, 11.0 parts by weight of acrylonitrile, and 0.193 parts by weight of t-dodecyl mercaptan was added dropwise over 3.5 hours. After polymerization was complete, the resulting graft copolymer (A-3) latex was cooled to 40°C, and 0.5 parts by weight of the reaction product of p-cresol, dicyclopentadiene, and isobutylene and 0.04 parts by weight of the phosphate ester compound (E1-1) were added with stirring. The mixture was then coagulated with 1.5% by mass of sulfuric acid, neutralized with sodium hydroxide, washed, centrifuged, and dried to obtain a graft copolymer (A-3) containing a phosphate ester compound (E1-1) (monomer ratio: styrene 73% by mass, acrylonitrile 27% by mass). The graft ratio of the resulting graft copolymer (A-3) was 38%.

[0139] (Production Example 4) Graft copolymer (A-4) containing phosphoric acid ester compound (E1-1) A phosphate ester compound (E1-1)-containing graft copolymer (A-4) was obtained in the same manner as in Production Example 3, except that the amount of the phosphate ester compound (E1-1) added was changed to 0.2 parts by mass.

[0140] (Production Example 5) Graft copolymer (A-5) containing phosphoric acid ester compound (E1-1) A graft copolymer (A-5) containing a phosphate ester compound (E1-1) was obtained in the same manner as in Production Example 3, except that the amount of the phosphate ester compound (E1-1) added was changed to 0.4 parts by mass.

[0141] (Production Example 6) Graft copolymer (A-6) containing phosphoric acid ester compound (E1-1) A graft copolymer (A-6) containing a phosphate ester compound (E1-1) was obtained in the same manner as in Production Example 3, except that the amount of the phosphate ester compound (E1-1) added was changed to 0.6 parts by mass.

[0142] (Production Example 7) Graft copolymer (A-7) containing phosphoric acid ester compound (E1-2) Graft copolymer (A-7) containing phosphate ester compound (E1-2) was obtained in the same manner as in Production Example 3, except that phosphate ester compound (E1-2) was used instead of phosphate ester compound (E1-1) and the amount added was changed to 0.2 parts by mass.

[0143] (Production Example 8) Polyoxyethylene alkylamine (E2-1)-containing graft copolymer (A-8) A polyoxyethylene alkylamine (E2-1)-containing graft copolymer (A-8) was obtained in the same manner as in Production Example 3, except that SN Wet S (E2-1) manufactured by San Nopco Ltd. was used instead of the phosphate ester compound (E1-1) and the amount added was changed to 0.06 parts by mass.

[0144] (Production Example 9) Polyoxyethylene alkylamine (E2-1)-containing graft copolymer (A-9) A polyoxyethylene alkylamine (E2-1)-containing graft copolymer (A-9) was obtained in the same manner as in Production Example 3, except that SN Wet S (E2-1) manufactured by San Nopco Ltd. was used instead of the phosphate ester compound (E1-1) and the amount added was 0.3 parts by mass.

[0145] (Production Example 10) Polyoxyethylene alkylamine (E2-1)-containing graft copolymer (A-10) A polyoxyethylene alkylamine (E2-1)-containing graft copolymer (A-10) was obtained in the same manner as in Production Example 3, except that SN Wet S (E2-1) manufactured by San Nopco Ltd. was used instead of the phosphate ester compound (E1-1) and the amount added was 0.6 parts by mass.

[0146] (Production Example 11) Polyoxyethylene alkylamine (E2-1)-containing graft copolymer (A-11) A polyoxyethylene alkylamine (E2-1)-containing graft copolymer (A-11) was obtained in the same manner as in Production Example 3, except that SN Wet S (E2-1) manufactured by San Nopco Ltd. was used instead of the phosphate ester compound (E1-1) and the amount added was 0.9 parts by mass.

[0147] (Production Example 12) Graft copolymer (A-12) containing phosphoric acid ester compound (E1-1) and polyoxyethylene alkylamine (E2-1) A graft copolymer (A-12) containing a phosphate ester compound (E1-1) and a polyoxyethylene alkylamine (E2-1) was obtained in the same manner as in Production Example 3, except that the amount of the phosphate ester compound (E1-1) added was changed to 0.1 parts by mass and 0.15 parts by mass of SN Wet S (E2-1) manufactured by San Nopco Ltd. was mixed and added.

[0148] (Production Example 13) Graft copolymer (A-13) A graft copolymer (A-13) was obtained in the same manner as in Production Example 3, except that the phosphate ester compound (E1-1) was not added.

[0149] (Production Example 14) Graft copolymer (A-14) Graft copolymer (A-14) was obtained in the same manner as in Production Example 1, except that the phosphate ester compound (E1-1) was not added.

[0150] (Production Example 15) Graft copolymer (A-15) containing phosphoric acid ester compound (E1-1) A graft copolymer (A-15) containing a phosphate ester compound (E1-1) was obtained in the same manner as in Production Example 1, except that the amount of the phosphate ester compound (E1-1) added was changed to 0.02 parts by mass.

[0151] (Production Example 16) Polyoxyethylene alkylamine (E2-1)-containing graft copolymer (A-16) A polyoxyethylene alkylamine (E2-1)-containing graft copolymer (A-16) was obtained in the same manner as in Production Example 1, except that SN Wet S (E2-1) manufactured by San Nopco Ltd. was used instead of the phosphate ester compound (E1-1) and the amount added was 0.03 parts by mass.

[0152] (Production Example 17) Graft copolymer (A-17) containing phosphoric acid ester compound (E1-1) A graft copolymer (A-17) containing a phosphate ester compound (E1-1) was obtained in the same manner as in Production Example 3, except that the amount of the phosphate ester compound (E1-1) added was changed to 0.02 parts by mass.

[0153] (Production Example 18) Polyoxyethylene alkylamine (E2-1)-containing graft copolymer (A-18) A polyoxyethylene alkylamine (E2-1)-containing graft copolymer (A-18) was obtained in the same manner as in Production Example 3, except that SN Wet S (E2-1) manufactured by San Nopco Ltd. was used instead of the phosphate ester compound (E1-1) and the amount added was 0.03 parts by mass.

[0154] Vinyl copolymer (B): (Production Example 19) Vinyl copolymer (B-1) 2m condenser for vaporization and carbonization of monomer vapor with helical ribbon blades 3 Using a continuous bulk polymerization apparatus comprising a complete mixing type polymerization tank, a single screw extruder type preheater, and a twin screw extruder type demonomerizer, a vinyl copolymer (B-1) was produced by the following method.

[0155] First, a monomer mixture (b) consisting of 72 parts by mass of styrene, 28 parts by mass of acrylonitrile, 0.2 parts by mass of n-octyl mercaptan, and 0.015 parts by mass of 1,1-bis(t-butylperoxy)cyclohexane was continuously fed to a complete mixing polymerization tank at a rate of 150 kg / h, and continuous bulk polymerization was carried out while maintaining the polymerization temperature at 130°C and the tank pressure at 0.08 MPa. The conversion of the polymerization reaction mixture at the outlet of the complete mixing polymerization tank was controlled to 65±3%.

[0156] Next, the polymerization reaction mixture was preheated using a single-screw extruder preheater and then fed to a twin-screw extruder demonomerizer. Unreacted monomer was evaporated under reduced pressure and recovered from the vent of the twin-screw extruder demonomerizer. The recovered unreacted monomer was continuously refluxed back to the complete mixing polymerization tank. The styrene / acrylonitrile copolymer with an apparent conversion of 99% or more was melt-kneaded at 150 kg / h. The melt-kneaded product was extruded into strands and cut with a cutter to obtain a 3 mm-long vinyl copolymer (B-1) (monomer ratio: styrene 72% by mass, acrylonitrile 28% by mass). The weight-average molecular weight of the resulting vinyl copolymer (B-1) was 128,000.

[0157] (Examples 1 to 13, Comparative Examples 1 to 6) Graft copolymer (A), vinyl copolymer (B), phosphate ester compound (E1), polyoxyethylene alkylamine (E2) in the amounts shown in Table 1 or Table 2, 0.8 parts by mass of carbon black, 1 part by mass of ethylene bisstearamide, 0.3 parts by mass of bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 0.3 parts by mass of phenol, 2-(2H-benzotriazol-2-yl)-4-methyl, and 0.15 parts by mass of octadecyl-3-(3,5-di-tetrabutyl-4-hydroxyphenyl) propionate were blended, and the resulting mixture was melt-kneaded in a co-rotating twin-screw extruder with a screw diameter of 30 mm (temperature range: 240 to 260 ° C.) to obtain pellets. In Example 13, 0.1 parts by mass of phosphate ester compound (E1-1) was added during blending.

[0158] [Table 1]

[0159] [Table 2]

[0160] The resin compositions of Examples 1 to 13 have a Charpy impact strength of 10 kJ / m 2The resin compositions of Examples 1 to 5, 7 to 9, and 12 contained a phosphate ester compound (E1) and / or a polyoxyethylene alkylamine (E2) in a total amount of 60 ppm (mass / mass) to 600 ppm (mass / mass) per 100 parts by mass of the entire resin composition, and the amount of either or both of the phosphate ester compound (E1) and / or the polyoxyethylene alkylamine (E2) was 0.04 parts by mass to 0.5 parts by mass per 100 parts by mass of the graft copolymer (A). The gloss was further improved to 85% or more, and a significant decrease in the latex morphology and volatility were suppressed.

[0161] On the other hand, the resin compositions of Comparative Examples 1 to 6 contained either or both of the phosphate ester compound (E1) and the polyoxyethylene alkylamine (E2) in a total amount of less than 60 ppm (mass / mass) per 100 parts by mass of the total amount of the entire resin composition, and had poor appearance. Furthermore, the color development properties of Comparative Examples 4 to 6 were also poor.

[0162] (Production Example 20) Graft copolymer (A-19) containing phosphoric acid ester compound (E1-1) A graft copolymer (A-19) containing a phosphate ester compound (E1-1) was obtained in the same manner as in Production Example 3, except that the amount of the phosphate ester compound (E1-1) added was changed to 0.1 parts by mass.

[0163] (Production Example 21) Graft copolymer (A-20) containing phosphoric acid ester compound (E1-1) A graft copolymer (A-20) containing a phosphate ester compound (E1-1) was obtained in the same manner as in Production Example 3, except that the amount of the phosphate ester compound (E1-1) added was changed to 0.05 parts by mass.

[0164] (Production Example 22) Vinyl copolymer (B-2) 2m condenser for vaporization and carbonization of monomer vapor with helical ribbon blades 3 Using a continuous bulk polymerization apparatus comprising a complete mixing type polymerization tank, a single screw extruder type preheater, and a twin screw extruder type demonomerizer, a vinyl copolymer (B-2) was produced by the following method.

[0165] First, a monomer mixture (b) consisting of 65 parts by mass of styrene, 35 parts by mass of acrylonitrile, 0.25 parts by mass of n-octyl mercaptan, and 0.016 parts by mass of 1,1-bis(t-butylperoxy)cyclohexane was continuously fed to a complete mixing polymerization tank at a rate of 150 kg / h, and continuous bulk polymerization was carried out while maintaining the polymerization temperature at 130°C and the tank pressure at 0.08 MPa. The conversion of the polymerization reaction mixture at the outlet of the complete mixing polymerization tank was controlled to 65±3%.

[0166] Next, the polymerization reaction mixture was preheated using a single-screw extruder preheater and then fed to a twin-screw extruder demonomerizer. Unreacted monomer was evaporated under reduced pressure and recovered from the vent of the twin-screw extruder demonomerizer. The recovered unreacted monomer was continuously refluxed to the complete mixing polymerization tank. The styrene / acrylonitrile copolymer with an apparent conversion of 99% or more was melt-kneaded at 150 kg / h. The melt-kneaded product was extruded into strands and cut with a cutter to obtain a 3 mm-long vinyl copolymer (B-2) (monomer ratio: styrene 66% by mass, acrylonitrile 34% by mass). The weight-average molecular weight of the resulting vinyl copolymer (B-2) was 140,000.

[0167] (Production Example 23) Heat-resistant vinyl copolymer (C-1) A 30L autoclave equipped with a stirrer was charged with 65 parts by weight of styrene, 7 parts by weight of maleic anhydride, 0.3 parts by weight of 2,4-diphenyl-4-methyl-1-pentene, and 25 parts by weight of methyl ethyl ketone. After purging the system with nitrogen gas, the temperature was raised to 92°C, and a solution of 28 parts by weight of maleic anhydride and 0.18 parts by weight of t-butyl peroxy-2-ethylhexanoate in 100 parts by weight of methyl ethyl ketone was continuously added over 7 hours. After the addition, 0.03 parts by weight of t-butyl peroxy-2-ethylhexanoate was added, the temperature was raised to 120°C, and the reaction was continued for another 1 hour to obtain a polymer solution of styrene-maleic anhydride copolymer. Next, 32 parts by weight of aniline and 0.6 parts by weight of triethylamine were added to the polymer solution and the reaction was continued at 140°C for 7 hours. The polymer solution after the imidization reaction was fed to a vent-type screw extruder, and the volatile components were removed to obtain a pellet-shaped heat-resistant vinyl copolymer (C-1) (monomer ratio: styrene 51% by mass, N-phenylmaleimide 48% by mass, maleic anhydride 1% by mass). The reduced viscosity (ηsp / c) of the obtained heat-resistant vinyl copolymer (C-1) was 0.46 dL / g.

[0168] (Examples 14 to 19, Comparative Examples 7 to 8) Graft copolymer (A), vinyl copolymer (B), heat-resistant vinyl copolymer (C), phosphate ester compound (E1), and polyoxyethylene alkylamine (E2) were blended in the amounts shown in Table 3. Also, 0.9 parts by mass of carbon black, 0.6 parts by mass of ethylene bisstearic acid amide, 0.3 parts by mass of bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, and 0.3 parts by mass of octadecyl-3-(3,5-di-tetrabutyl-4-hydroxyphenyl) propionate were blended, and the resulting mixture was melt-kneaded in a co-rotating twin-screw extruder with a screw diameter of 30 mm (temperature range: 260 to 290°C) to obtain pellets.

[0169] [Table 3]

[0170] The resin compositions of Examples 14 to 19 have a Charpy impact strength of 6 kJ / m 2 The resin compositions of Examples 14 to 17 had a tensile elongation of 19% or more, a gloss of 88% or more, an L value of 7 or less, and a heat distortion temperature of 96°C or more, and while maintaining impact resistance and high tensile elongation, they eliminated deterioration in appearance, had good color development, and were further imparted with heat resistance. The resin compositions of Examples 14 to 17 contained a phosphate ester compound (E1) and / or a polyoxyethylene alkylamine (E2) in a total amount of 60 ppm (mass / mass) to 600 ppm (mass / mass) per 100 parts by mass of the entire resin composition, and the amount of either / both of the phosphate ester compound (E1) and / or the polyoxyethylene alkylamine (E2) added was 0.04 parts by mass to 0.5 parts by mass per 100 parts by mass of the graft copolymer (A), thereby preventing a significant deterioration in the properties of the latex and also preventing a significant decrease in volatility.

[0171] On the other hand, the resin compositions of Comparative Examples 7 and 8 contained either or both of the phosphate ester compound (E1) and the polyoxyethylene alkylamine (E2) in a total amount of less than 60 ppm (mass / mass) per 100 parts by mass of the total amount of the entire resin composition, and were insufficient in terms of tensile elongation and had poor appearance and color development.

[0172] Furthermore, when the morphology of the resin composition was confirmed, it was found that in Example 14, the white areas representing the acrylic rubbery polymer were finely dispersed, as shown in Figure 1. In Comparative Example 7, the white areas representing the acrylic rubbery polymer were more concentrated than in Figure 1, as shown in Figure 2, suggesting aggregation of the rubber. [Industrial Applicability]

[0173] The resin composition of the present invention and molded articles using the same can be widely used in fields such as home appliances, general merchandise, and automotive materials.

Claims

1. A resin composition comprising: a graft copolymer (A) obtained by graft copolymerizing a monomer mixture (a) containing at least an aromatic vinyl monomer (a1) and a vinyl cyanide monomer (a2) in the presence of a rubber polymer (r); a vinyl copolymer (B) obtained by copolymerizing a monomer mixture (b) containing at least an aromatic vinyl monomer (b1) and a vinyl cyanide monomer (b2); and either or both of a phosphoric acid ester compound (E1) represented by the following chemical formula (1) and a polyoxyethylene alkylamine (E2) represented by the following chemical formula (2), wherein the ratio of the total amount of the phosphoric acid ester compound (E1) and the polyoxyethylene alkylamine (E2) to the total amount of the entire resin composition is 60 ppm (mass / mass) or more. 【Chemistry 1】 (R is an alkyl or alkenyl group having 8 to 22 carbon atoms, AO is an oxyalkylene group having 2 or 3 carbon atoms, n is an integer from 1 to 20, m is an integer of 1 or 2, M is a hydrogen atom, a Group 1 metal atom or a Group 2 metal atom, and q is 1 when M is a hydrogen atom or a Group 1 metal atom, or 1 / 2 when M is a Group 2 metal atom.) 【Chemistry 2】 (wherein R represents an alkyl group or alkenyl group having 8 to 22 carbon atoms, and m and n are positive integers satisfying the relationship 2<m+n≦20.)

2. 2. The resin composition according to claim 1, wherein the rubbery polymer (r) is one or both of a polybutadiene rubber and an acrylic rubber.

3. The resin composition according to claim 1 or 2, further comprising a heat-resistant vinyl copolymer (C) obtained by copolymerizing a vinyl monomer mixture (c) containing at least an aromatic vinyl monomer (c1) and a maleimide monomer (c2).

4. a step of graft copolymerizing a monomer mixture (a) containing at least an aromatic vinyl monomer (a1) and a vinyl cyanide monomer (a2) in the presence of a rubber polymer (r) to obtain an emulsion-polymerized latex; a step of adding either or both of a phosphoric acid ester compound (E1) and a polyoxyethylene alkylamine (E2) to the emulsion-polymerized latex; and a step of subsequently contacting the emulsion-polymerized latex with an aqueous sulfuric acid solution to obtain a graft copolymer (A) (Step A); a step (step B) of obtaining a vinyl copolymer (B) obtained by copolymerizing a monomer mixture (b) containing at least an aromatic vinyl monomer (b1) and a vinyl cyanide monomer (b2); a step (step C) of obtaining a heat-resistant vinyl copolymer (C) obtained by copolymerizing a vinyl monomer mixture (c) containing at least an aromatic vinyl monomer (c1) and a maleimide monomer (c2) as necessary; A method for producing a resin composition, comprising a step of mixing the graft copolymer (A), the vinyl copolymer (B), and the heat-resistant vinyl copolymer (C) obtained in the steps A, B, and C (provided that the heat-resistant vinyl copolymer (C) is an optional component), a method for producing a resin composition, characterized in that the total amount of a phosphate ester compound (E1) and a polyoxyethylene alkylamine (E2) is adjusted to a ratio of 60 ppm (mass / mass) or more relative to the total amount of the entire resin composition.

5. 6. The method for producing a resin composition according to claim 5, wherein, in the step A, a phosphate ester compound (E1) is used in which, when the mass of the phosphate ester compound (E1) is taken as 100 mass%, a content of Group 2 metal atoms in the phosphate ester compound (E1) is 2 mass% or more and 5 mass% or less.

6. A molded article obtained by molding the resin composition according to any one of claims 1 to 3 or the resin composition obtained by the method for producing a resin composition according to claim 4 or 5.

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