Thermoplastic resin composition and molded article

Abstract

This thermoplastic resin composition contains a thermoplastic resin comprising: (A) a polycarbonate resin containing a polycarbonate-polyorganosiloxane copolymer (A1) having a portion (a1) composed of a polycarbonate and a portion (a2) composed of a polyorganosiloxane; (B) a rubbery polymer-reinforced vinyl-based resin containing a graft resin (B1) obtained by polymerizing a vinyl-based monomer in the presence of a composite rubber having a polymer portion (b1) containing a structural unit derived from an alkyl (meth)acrylate ester and a portion (b2) composed of a polyorganosiloxane; and (C) a vinyl-based resin containing a structural unit derived from an aromatic vinyl compound and a structural unit derived from a vinyl cyanide compound.

Description

Thermoplastic resin composition and molded article

[0001] The present invention relates to a thermoplastic resin composition that provides molded articles with excellent impact resistance and weather resistance at low temperatures. In this specification, "low temperature" means a temperature of -30°C or lower.

[0002] Polycarbonate resin (PC resin) is widely used as a raw material for manufacturing housings (exteriors) or peripheral components of office automation equipment, electrical and electronic equipment, optical equipment, and other components of building materials, medical equipment, and vehicles, due to its excellent heat resistance and other mechanical properties such as impact resistance.

[0003] In recent years, the applications of resin compositions containing polycarbonate resin have been expanding. For example, molded articles made from such resin compositions, or structures equipped with them, can be used not only at room temperature but also in cold regions with low temperatures, environments where temperatures drop at night, and other diverse usage conditions.

[0004] Conventionally, a polycarbonate-based resin composition is known that has low-temperature impact properties, comprising 100 parts by mass of a resin mixture containing 30 to 100% by mass of a polycarbonate-polyorganosiloxane copolymer (A-1) having structural units represented by general formula (I) and structural units represented by general formula (II), and having an average number of repeating units n of organosiloxane constituent units in general formula (II) of 50 to 500, and 0 to 70% by mass of an aromatic polycarbonate other than (A-1) (A-2), and containing 1 to 5.5 parts by mass of (B) polyorganosiloxane-acrylic composite rubber, with a viscosity-average molecular weight of 17,000 to 23,000 (see Patent Document 1). [In the formula, R １ and R ２ Each of these independently represents an alkyl or alkoxy group having 1 to 6 carbon atoms, where X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, -S-, -SO-, -SO ２ R represents -, -O-, or -CO-, where a and b each independently represent integers from 0 to 4. ３ ~R ６Each of these independently represents a hydrogen atom, a halogen atom, or a C1-C6 alkyl group, a C1-C6 alkoxy group, or a C6-C12 aryl group; Y represents an organic residue containing aliphatic or aromatic compounds; and n represents the average number of repetitions.

[0005] Furthermore, as resin compositions with excellent impact resistance and fluidity, there are known polycarbonate resins (S) that include a polycarbonate-polyorganosiloxane copolymer (A) containing a polycarbonate block and a polyorganosiloxane block, and another aromatic polycarbonate resin (B), as well as polycarbonate resin compositions that contain a styrene resin (C) such as acrylonitrile-styrene copolymer or ABS resin in a specific proportion (see Patent Document 2).

[0006] Japanese Patent Publication No. 2014-58607WO2018 / 159781

[0007] For example, when a molded product is manufactured using the resin composition disclosed in Patent Document 2, which contains ABS resin as the styrene-based resin (C), the weather resistance is insufficient, and pearlescent gloss unevenness sometimes appears on the surface. When manufacturing colored components, generally, considering the variation in color, a method is applied in which a colorless molded product without a coloring agent is manufactured first, and then a coloring paint is applied to this colorless molded product. On the other hand, from the viewpoint of cost reduction, attempts have been made to directly manufacture colored molded products, but even when a coloring agent is added to the resin composition disclosed in Patent Document 2, which contains ABS resin as the styrene-based resin (C), colored molded products with unsuppressed gloss unevenness sometimes appear.

[0008] The object of the present invention is to provide a thermoplastic resin composition that gives a molded product having a good molded appearance without gloss unevenness, and excellent low-temperature impact resistance and weather resistance.

[0009] The present inventors have found that the above problems can be solved by using a thermoplastic resin composition containing a modified polycarbonate resin which is a polycarbonate-polyorganosiloxane copolymer having a portion made of polycarbonate and a portion made of polyorganosiloxane, a graft resin obtained by polymerizing vinyl monomers in the presence of a composite rubber having a polymer portion containing structural units derived from (meth)acrylate alkyl ester and a portion made of polyorganosiloxane, and a vinyl resin containing structural units derived from aromatic vinyl compounds and structural units derived from vinyl cyanide compounds, wherein the amount of the latter structural units is within a specific range, and have thus completed the present invention.

[0010] The present invention is as follows: [1] A thermoplastic resin composition comprising (A) a polycarbonate resin, (B) a rubber polymer-reinforced vinyl resin obtained by polymerizing vinyl monomers in the presence of a rubber polymer, and (C) a vinyl resin (excluding the rubber polymer-reinforced vinyl resin (B)), wherein the polycarbonate resin (A) comprises a polycarbonate-polyorganosiloxane copolymer (A1) having a portion made of polycarbonate (a1) and a portion made of polyorganosiloxane (a2), and the rubber polymer-reinforced vinyl resin (B) comprises a graft resin (B1) obtained by polymerizing vinyl monomers in the presence of a composite rubber having a polymer portion (b1) containing structural units derived from an alkyl (meth)acrylate and a portion made of polyorganosiloxane (b2), A thermoplastic resin composition characterized in that the vinyl resin (C) contains structural units (c1) derived from an aromatic vinyl compound and structural units (c2) derived from a vinyl cyanide compound, the content ratio of the structural units (c2) is 18 to 40% by mass relative to the vinyl resin (C), and the ratio of the total amount of each polyorganosiloxane derived from the polycarbonate / polyorganosiloxane copolymer (A1) and the graft resin (B1) to the total amount of the thermoplastic resin is 1.5 to 10.0% by mass. [2] The thermoplastic resin composition according to [1], wherein the content ratio of the composite rubber derived from the graft resin (B1) relative to the thermoplastic resin is 1.0 to 10.0% by mass. [3] The thermoplastic resin composition according to [1] or [2], wherein the volume average particle diameter of the graft resin (B1) is 80 to 300 nm. [4] The thermoplastic resin composition according to any one of the above [1] to [3], wherein the absolute value of the difference between the refractive index of the polycarbonate resin (A) and the refractive index of the vinyl resin (C) is 0.05 or less. [5] The thermoplastic resin composition according to any one of the above [1] to [4], wherein the content ratios of the polycarbonate resin (A), the rubber polymer-reinforced vinyl resin (B), and the vinyl resin (C) are 60 to 90% by mass, 3 to 20% by mass, and 3 to 30% by mass, respectively, when the total of these is 100% by mass.[6] The thermoplastic resin composition according to any one of [1] to [5] above, wherein the content of the portion (a2) consisting of polyorganosiloxane constituting the polycarbonate / polyorganosiloxane copolymer (A1) is 2 to 15% by mass relative to the polycarbonate resin (A). [7] The thermoplastic resin composition according to any one of [1] to [6] above, wherein the content of the portion (b2) consisting of polyorganosiloxane constituting the graft resin (B1) is 2 to 15% by mass relative to the rubbery polymer-reinforced vinyl resin (B). [8] A molded article characterized by containing the thermoplastic resin composition according to any one of [1] to [7] above. [9] The molded article according to [8] above, wherein the content of Si element is 1.35% by mass or more.

[0011] By using the thermoplastic resin composition of the present invention, it is possible to obtain molded articles that have a good molded appearance without gloss unevenness, and that exhibit excellent low-temperature impact resistance and weather resistance. The molded articles of the present invention can be suitably used in both enclosed and outdoor environments where low-temperature conditions may occur, and are useful, for example, as interior components in vehicles, ships, aircraft, etc., as components (such as housings) in office automation equipment, home appliances, electrical and electronic equipment, building materials, etc., and as components in agricultural materials, daily necessities, sporting goods, stationery, etc.

[0012] The present invention will be described in detail below. In this specification, "(meth)acrylic" means acrylic and methacrylic, "(meth)acrylate" means acrylate and methacrylate, "(meth)acryloyl" means acryloyl and methacryloyl, and "(co)polymer" means homopolymer and copolymer.

[0013] The thermoplastic resin composition of the present invention is a composition containing a thermoplastic resin comprising a polycarbonate resin (A), a rubbery polymer-reinforced vinyl resin (B) obtained by polymerizing a vinyl monomer in the presence of a rubbery polymer, and a vinyl resin (C) excluding said rubbery polymer-reinforced vinyl resin (B), all of which have specific structures. In the thermoplastic resin composition of the present invention, the thermoplastic resin may further contain other resins (described later) as necessary. In addition, the thermoplastic resin composition of the present invention may contain various additives (described later) in addition to the thermoplastic resin.

[0014] The polycarbonate resin (A) according to the present invention is a component that includes a polycarbonate-polyorganosiloxane copolymer (A1) having a portion (a1) composed of polycarbonate and a portion (a2) composed of polyorganosiloxane, and may further contain another polycarbonate resin (hereinafter referred to as "polycarbonate resin (A2)").

[0015] First, the polycarbonate-polyorganosiloxane copolymer (A1) will be described. The portion (a1) preferably contains a structural unit represented by the following general formula (1), and the portion (a2) preferably contains a structural unit represented by the following general formula (2). (In the formula, R １ and R ２ each independently represent a halogen atom, an optionally substituted hydrocarbon group or an alkoxy group; X represents a single bond, a divalent hydrocarbon group, an oxygen atom, a sulfur atom, -SO-, -SO ２ -, or -CO-; and p and q each independently represent an integer of 0 to 4.) (In the formula, R ３ and R ４ each independently represent a hydrogen atom, a halogen atom, an optionally substituted hydrocarbon group, or an alkoxy group.)

[0016] In the general formula (1) representing the structural unit contained in the portion (a1), R １ and R ２Each of these is independently a halogen atom, a hydrocarbon group which may have substituents, or an alkoxy group. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms. The hydrocarbon group can be an alkyl group, an aryl group, or an aralkyl group. In the case of an alkyl group, it may be linear or branched, and the number of carbon atoms is preferably 1 to 6, more preferably 1 to 4. The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms. １ and R ２ These may be the same or different from each other. p and q are each an integer between 0 and 4, preferably between 0 and 2, more preferably 0 or 1. When p is an integer between 2 and 4, each R １ These may be the same or different from each other. Also, if q is an integer between 2 and 4, each R ２ They may be identical to each other, or they may be different.

[0017] In the general formula (1) above, X is a single bond, a divalent hydrocarbon group, an oxygen atom, a sulfur atom, -SO-, -SO ２ It is - or -CO-. Examples of divalent hydrocarbon groups include alkylene groups, alkylidene groups, cycloalkylene groups, cycloalkylidene groups, fluoranyl groups, arylalkylene groups, and arylalkylidene groups. The alkylene group is a linear or branched alkylene group having preferably 1 to 8 carbon atoms, more preferably 1 to 5. The alkylidene group is a linear or branched alkylidene group having preferably 2 to 8 carbon atoms. The cycloalkylene group is a cycloalkylene group having preferably 5 to 15 carbon atoms, more preferably 5 to 10. The cycloalkylidene group is a cycloalkylidene group having preferably 5 to 15 carbon atoms, more preferably 5 to 10, and particularly preferably 5 to 8 carbon atoms, and examples include cyclohexylidene groups, 3,5,5-trimethylcyclohexylidene groups, and 2-adamantylidene groups. The aryl portion in arylalkylene groups and arylalkylidene groups can be aryl groups having 6 to 14 ring-forming carbon atoms, such as phenyl groups, naphthyl groups, biphenyl groups, and anthryl groups.

[0018] The type of the structural unit represented by the above general formula (1) contained in the above part (a1) is not particularly limited, and may be only one type, or may be two or more types.

[0019] In addition, the content ratio of the part (a1) contained in the above polycarbonate-polyorganosiloxane copolymer (A1) is preferably 85 to 98% by mass, more preferably 90 to 98% by mass, still more preferably 94 to 98% by mass, from the viewpoints of the impact resistance of the composition and the color developability when the composition contains a colorant.

[0020] In the general formula (2) representing the structural unit contained in the above part (a2), R ３ and R ４ are each independently a hydrogen atom, a halogen atom, an optionally substituted hydrocarbon group, or an alkoxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The hydrocarbon group may be an alkyl group, an aryl group or an aralkyl group. In the case of an alkyl group, it may be linear or branched, and the number of carbon atoms is preferably 1 to 6, more preferably 1 to 4, and particularly preferably 1. The aryl group is preferably an aryl group having 6 to 12 carbon atoms. In addition, the alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms. R ３ and R ４ may be the same as or different from each other.

[0021] The type of the structural unit represented by the above general formula (2) contained in the above part (a2) is not particularly limited, and may be only one type, or may be two or more types.

[0022] In addition, the content ratio of the part (a2) contained in the above polycarbonate-polyorganosiloxane copolymer (A1) is preferably 2 to 15% by mass, more preferably 2 to 10% by mass, still more preferably 2 to 6% by mass, from the viewpoints of low-temperature impact resistance and weather resistance of the composition.

[0023] The weight average molecular weight (hereinafter referred to as "Mw") of the polycarbonate-polyorganosiloxane copolymer (A1) is not particularly limited, but from the viewpoint of impact resistance of the composition, it is preferably 10,000 to 100,000, more preferably 20,000 to 70,000. In addition, this Mw can be measured by gel permeation chromatography (GPC).

[0024] The refractive index of the polycarbonate-polyorganosiloxane copolymer (A1) (hereinafter, "n Ａ ") is preferably 1.555 to 1.590, more preferably 1.560 to 1.575, still more preferably 1.565 to 1.575. In addition, this refractive index means the refractive index of light at a temperature of 23°C and a wavelength of 589 nm (the same applies hereinafter).

[0025] The polycarbonate-polyorganosiloxane copolymer (A1) contained in the thermoplastic resin composition of the present invention may be used alone or in combination of two or more. The content of the polycarbonate-polyorganosiloxane copolymer (A1) contained in the polycarbonate resin (A) is preferably 2% by mass or more, more preferably 5% by mass or more, and the upper limit is usually 20% by mass.

[0026] The polycarbonate-polyorganosiloxane copolymer (A1) can be conventionally produced by a known method. For example, an aromatic polycarbonate oligomer is reacted with a polyorganosiloxane having a reactive group (o-allylphenol residue, p-hydroxystyrene residue, eugenol residue, etc.) at the terminal constituting the moiety (a2) (segment). It can be obtained by dissolving in a solvent (methylene chloride, chlorobenzene, chloroform, etc.), adding a dihydric phenol such as bisphenol A in the presence of a catalyst such as a tertiary amine (triethylamine, etc.), a quaternary ammonium salt (trimethylbenzylammonium chloride, etc.), and carrying out an interfacial polycondensation reaction. In the polycarbonate-polyorganosiloxane copolymer thus obtained, the degree of polymerization of the moiety (a1) is preferably about 3 to 100, and the degree of polymerization of the moiety (a2) is preferably about 2 to 500.

[0027] Next, the polycarbonate resin (A2) is not particularly limited as long as it is a polycarbonate resin having carbonate bonds in its main chain and not containing polyorganosiloxane moieties, and may be any of aromatic polycarbonates, alicyclic polycarbonates, or aliphatic polycarbonates. These may also be used in combination. In the present invention, aromatic polycarbonates are preferred from the viewpoint of mechanical properties and heat resistance.

[0028] As the aromatic polycarbonate mentioned above, you can use one obtained by transesterification (transesterification reaction) of aromatic dihydroxy compounds and diester carbonates by melting, one obtained by interfacial polycondensation using phosgene, or one obtained by the pyridine method using the reaction product of pyridine and phosgene.

[0029] Aromatic dihydroxy compounds can be any compound having two hydroxyl groups in its molecule, such as hydroquinone, resorcinol, dihydroxybenzene, 4,4'-biphenol, 2,2-bis(4-hydroxyphenyl)propane (hereinafter referred to as "bisphenol A"), 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl-3-methylphenyl)propane, 2,2-bis(3-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)methane, 1,1-bis(p-hydroxyphenyl)ethane, 2,2-bis(p-hydroxyphenyl)butane, 2,2-bis(p-hydroxyphenyl)pentane, 1,1-bis(p-hydroxyphenyl)cyclohexane, and 1,1-bis(p-hydroxyphenyl)-4-isopropyl Examples include pyrcyclohexane, 1,1-bis(p-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(p-hydroxyphenyl)-1-phenylethane, 9,9-bis(p-hydroxyphenyl)fluorene, 9,9-bis(p-hydroxy-3-methylphenyl)fluorene, 4,4'-(p-phenylenediisopropylidene)bisphenol, 4,4'-(m-phenylenediisopropylidene)bisphenol, bis(p-hydroxyphenyl)oxide, bis(p-hydroxyphenyl)ketone, bis(p-hydroxyphenyl)ether, bis(p-hydroxyphenyl)ester, bis(p-hydroxyphenyl)sulfide, bis(p-hydroxyphenyl)sulfide, bis(p-hydroxyphenyl)sulfone, bis(3,5-dibromo-4-hydroxyphenyl)sulfone, and bis(p-hydroxyphenyl)sulfoxide. These can be used individually or in combination of two or more.

[0030] Among the aromatic hydroxy compounds described above, compounds having a hydrocarbon group between two benzene rings are preferred. In this compound, the hydrocarbon group may be a halogen-substituted hydrocarbon group. Furthermore, the benzene ring may have hydrogen atoms substituted with halogen atoms. Accordingly, examples of the preferred compounds include bisphenol A, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl-3-methylphenyl)propane, 2,2-bis(3-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)methane, 1,1-bis(p-hydroxyphenyl)ethane, and 2,2-bis(p-hydroxyphenyl)butane. Of these, bisphenol A is particularly preferred.

[0031] Examples of diester carbonates used to obtain aromatic polycarbonates by transesterification include dimethyl carbonate, diethyl carbonate, di-tert-butyl carbonate, diphenyl carbonate, and ditril carbonate. These can be used individually or in combination of two or more.

[0032] The average molecular weight and molecular weight distribution of the polycarbonate resin (A2) described above are not particularly limited, as long as the composition has moldability. The viscosity-average molecular weight (Mv) of the polycarbonate resin (A2) is preferably 10,000 to 32,000, more preferably 12,000 to 30,000, and even more preferably 15,000 to 25,000.

[0033] The rubber polymer-reinforced vinyl resin (B) according to the present invention is a graft resin obtained by polymerizing vinyl monomers in the presence of a rubber polymer, and includes a graft resin (B1) which is a composite rubber-reinforced vinyl resin obtained by polymerizing vinyl monomers in the presence of a composite rubber (hereinafter referred to as "composite rubber (v1)") having a polymer portion (b1) containing structural units derived from (meth)acrylate alkyl ester and a portion (b2) consisting of polyorganosiloxane, and may further include other rubber polymer-reinforced vinyl resins (hereinafter referred to as "graft resin (B2)").

[0034] First, the graft resin (B1) will be described. The composite rubber (v1) preferably has a structure in which a (meth)acrylic polymer (hereinafter referred to as "acrylic polymer rubber") with a glass transition temperature of preferably 25°C or lower, obtained by polymerizing a monomer containing an alkyl (meth)acrylate in the presence of a rubber made of polyorganosiloxane (hereinafter referred to as "polyorganosiloxane rubber"), and the polyorganosiloxane rubber are intertwined. In such a composite rubber (v1), the acrylic polymer rubber corresponds to the polymer portion (b1), and the polyorganosiloxane rubber corresponds to the portion (b2).

[0035] The molecular weight of the above-mentioned acrylic polymer rubber is not particularly limited, but Mw is preferably 20,000 to 200,000, and more preferably 50,000 to 150,000, from the viewpoint of the mechanical strength of the composition and the appearance of the resulting molded article.

[0036] The mass ratio of the polymer portion (b1) derived from acrylic polymer rubber and the portion (b2) derived from polyorganosiloxane rubber that constitute the composite rubber (v1) is not particularly limited. In the present invention, from the viewpoint of low-temperature impact resistance and weather resistance of the composition, if the composite rubber (v1) is 100% by mass, the content ratios of the polymer portion (b1) and portion (b2) are preferably 85 to 98% by mass and 2 to 15% by mass, more preferably 3 to 14% by mass and 5 to 12% by mass, even more preferably 86 to 97% by mass and 3 to 14% by mass, and even more preferably 88 to 95% by mass and 5 to 12% by mass, respectively.

[0037] The shape and size of the composite rubber (v1) described above are not particularly limited, but from the viewpoint of the low-temperature impact resistance of the composition and the color development when the composition contains a coloring agent, the volume-average particle diameter is preferably 50 to 300 nm, more preferably 80 to 200 nm. This volume-average particle diameter can be measured using a dynamic light scattering particle size distribution analyzer.

[0038] The composite rubber (v1) described above may be manufactured using conventionally known methods, such as those disclosed in Japanese Patent Application Publication No. 2019-19216.

[0039] The above-mentioned rubber polymer-reinforced vinyl resin (B) is a graft resin obtained by polymerizing vinyl monomers in the presence of a rubber polymer, as described above, where the rubber polymer constitutes the core portion and the vinyl monomer polymer constitutes the shell portion. The vinyl monomer preferably includes an aromatic vinyl compound and may further include at least one selected from vinyl cyanide compounds, (meth)acrylic acid ester compounds, maleimide compounds, unsaturated acid anhydrides, carboxyl group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds, etc. Therefore, the shell portion can consist of structural units derived from the aromatic vinyl compound and structural units derived from other monomers such as vinyl cyanide compounds. In the present invention, a particularly preferred embodiment of the shell portion is in which the vinyl monomer consists of an aromatic vinyl compound and a vinyl cyanide compound, and the shell portion consists of structural units derived from these monomers. The content ratio of structural units derived from the aromatic vinyl compound in the shell portion is preferably 60 to 85% by mass, more preferably 70 to 80% by mass, from the viewpoint of the mechanical strength and weather resistance of the composition.

[0040] Aromatic vinyl compounds are not particularly limited as long as they are compounds having at least one vinyl bond and at least one aromatic ring. Examples include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, β-methylstyrene, ethylstyrene, p-tert-butylstyrene, vinyltoluene, vinylxylene, vinylnaphthalene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, tribromostyrene, fluorostyrene, and the like. Of these, styrene and α-methylstyrene are preferred, and styrene is particularly preferred.

[0041] Examples of vinyl cyanide compounds include acrylonitrile, methacrylonitrile, ethacrylonitrile, α-ethylacrylonitrile, α-isopropylacrylonitrile, α-chloroacrylonitrile, and α-fluoroacrylonitrile.

[0042] Examples of (meth)acrylic acid ester compounds include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, hexyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl (meth)acrylate, and benzyl (meth)acrylate.

[0043] Examples of maleimide compounds include maleimide, N-methylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-dodecylmaleimide, N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(2,6-dimethylphenyl)maleimide, N-(2,6-diethylphenyl)maleimide, N-(2-methoxyphenyl)maleimide, N-benzylmaleimide, N-(4-hydroxyphenyl)maleimide, N-naphthylmaleimide, and N-cyclohexylmaleimide. Another method for introducing structural units derived from maleimide compounds into the graft resin (B1) is, for example, copolymerization of an unsaturated dicarboxylic acid anhydride of maleic anhydride followed by imidization.

[0044] Examples of the above unsaturated anhydrides include maleic anhydride, itaconic anhydride, and citraconic anhydride. Examples of the above carboxyl group-containing unsaturated compounds include (meth)acrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, and cinnamic acid.

[0045] The above hydroxyl group-containing unsaturated compounds include hydroxyl group-containing (meth)acrylic acid esters such as 2-hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and compounds obtained by adding ε-caprolactone to 2-hydroxyethyl (meth)acrylate; o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-α-methylstyrene, m-hydroxy-α Examples include methylstyrene, p-hydroxy-α-methylstyrene, 2-hydroxymethyl-α-methylstyrene, 3-hydroxymethyl-α-methylstyrene, 4-hydroxymethyl-α-methylstyrene, 4-hydroxymethyl-1-vinylnaphthalene, 7-hydroxymethyl-1-vinylnaphthalene, 8-hydroxymethyl-1-vinylnaphthalene, 4-hydroxymethyl-1-isopropenylnaphthalene, 7-hydroxymethyl-1-isopropenylnaphthalene, 8-hydroxymethyl-1-isopropenylnaphthalene, p-vinylbenzyl alcohol, 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, and 3-hydroxy-2-methyl-1-propene.

[0046] In a graft resin (B1) obtained by polymerizing a vinyl monomer in the presence of a composite rubber (v1) having a polymer portion (b1) and a portion (b2), the mass ratio of the shell portion derived from the vinyl monomer polymer to the core portion derived from the composite rubber (v1), i.e., the graft rate, is preferably 30 to 70% by mass, more preferably 40 to 60% by mass, from the viewpoint of the fluidity and weather resistance of the composition.

[0047] The shape and size of the graft resin (B1) described above are not particularly limited, but the volume-average particle size is preferably 80 to 300 nm, more preferably 80 to 300 nm, from the viewpoint of the mechanical strength of the composition and the appearance of the resulting molded article.

[0048] The graft resin (B1) contained in the thermoplastic resin composition of the present invention may be one type or two or more types. The content ratio of the graft resin (B1) contained in the rubbery polymer-reinforced vinyl resin (B) is preferably 30% by mass or more, more preferably 50% by mass or more, and the upper limit is usually 100% by mass.

[0049] The above-mentioned graft resin (B1) can be produced by subjecting a vinyl monomer to emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, etc., in the presence of composite rubber (v1). A preferred production method is emulsion polymerization using a polymerization initiator and an emulsifier.

[0050] Next, the graft resin (B2) is not particularly limited as long as it is obtained by polymerizing a vinyl monomer in the presence of a rubbery polymer other than the composite rubber (v1) (hereinafter referred to as "rubbery polymer (v2)"). Examples of rubbery polymer (v2) include diene rubber, ethylene-α-olefin copolymer rubber, and acrylic rubber. Conventionally known ABS resin, AES resin, ASA resin, etc., can be used as the graft resin (B2). In the above graft resin (B2), the mass ratio (graft rate) of the shell portion derived from the vinyl monomer polymer to the core portion derived from the rubbery polymer (v2) is not particularly limited. Furthermore, the shape and size of the above graft resin (B1) are not particularly limited.

[0051] The vinyl resin (C) according to the present invention is a resin that contains structural units (c1) derived from an aromatic vinyl compound and structural units (c2) derived from a vinyl cyanide compound, wherein the content ratio of structural units (c2) is within a specific range.

[0052] The vinyl resin (C) described above can be a copolymer consisting of structural unit (c1) and structural unit (c2), and further, it may be a copolymer consisting of structural unit (c1), structural unit (c2), and structural unit derived from another vinyl monomer (hereinafter referred to as "structural unit (c3)"). As the aromatic vinyl compound and vinyl cyanide compound, the compounds that can be used to form the rubber polymer-reinforced vinyl resin (B) described above can be applied. The aromatic vinyl compound is preferably styrene and α-methylstyrene, and particularly preferably styrene. The vinyl cyanide compound is preferably acrylonitrile. As other vinyl monomers, (meth)acrylic acid ester compounds, maleimide compounds, unsaturated acid anhydrides, carboxyl group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds, etc. can be used.

[0053] Regardless of its composition, the vinyl resin (C) according to the present invention has a content ratio of structural units (c2) of 10 to 40% by mass, preferably 15 to 30% by mass, and more preferably 19 to 25% by mass relative to the vinyl resin (C). When the vinyl resin (C) consists of structural units (c1), structural units (c2), and structural units (c3), their content ratios are preferably 60 to 85% by mass, 15 to 30% by mass, and 5 to 20% by mass, respectively, and more preferably 65 to 75% by mass, 19 to 25% by mass, and 5 to 20% by mass.

[0054] The Mw of the vinyl resin (C) described above is not particularly limited, but from the viewpoint of the fluidity and mechanical strength of the composition, it is preferably 50,000 to 300,000, and more preferably 100,000 to 200,000.

[0055] The refractive index of the above vinyl resin (C) (hereinafter referred to as "n") Ｃ The refractive index n of the polycarbonate resin (A) is preferably 1.555 to 1.590, more preferably 1.560 to 1.575, and even more preferably 1.565 to 1.575. Ａ and the refractive index n of vinyl resin (C) ＣThe absolute value of the difference is preferably 0.05 or less, and more preferably 0.01 or less, from the viewpoint of the appearance of the resulting molded product.

[0056] The vinyl resin (C) contained in the thermoplastic resin composition of the present invention may be one type or two or more types.

[0057] The proportions of polycarbonate resin (A), rubber polymer-reinforced vinyl resin (B), and vinyl resin (C) contained in the thermoplastic resin according to the present invention are preferably 60 to 95% by mass, 3 to 20% by mass, and 3 to 30% by mass, respectively, when the total of these is 100% by mass, more preferably 75 to 90% by mass, 3 to 10% by mass, and 5 to 20% by mass, respectively, from the viewpoint of the fluidity of the composition, impact resistance, weather resistance, and molded appearance.

[0058] As described above, the thermoplastic resin according to the present invention may include other resins. Examples of other resins include rubber polymer-reinforced vinyl resins (graft resins) obtained by polymerizing vinyl monomers in the presence of rubber polymers other than the composite rubber described above, vinyl (co)polymers containing structural units derived from either aromatic vinyl compounds or vinyl cyanide compounds, vinyl copolymers containing structural units derived from aromatic vinyl compounds and vinyl cyanide compounds that are not included in the vinyl resin (C) described above, polyvinyl chloride resins, polyvinylidene chloride resins, polyolefin resins, polyester resins, polycarbonate resins, polyarylate resins, polyamide resins, and the like. These can be used individually or in combination of two or more.

[0059] When the thermoplastic resin according to the present invention contains other resins, the proportion of those resins relative to the total amount of the thermoplastic resin is preferably 1 to 10% by mass, more preferably 2 to 5% by mass.

[0060] In the thermoplastic resin composition of the present invention, the ratio of the total amount of each polyorganosiloxane derived from the polycarbonate resin (A) and the rubbery polymer-reinforced vinyl resin (B) to the total amount of the thermoplastic resin is preferably 1.4 to 10.0% by mass, more preferably 1.4 to 5.0% by mass, from the viewpoint of the low-temperature impact resistance and weather resistance of the composition. The above ratio is determined by the silicon nuclear magnetic resonance spectrum ( ２９ Si-NMR analysis and proton nuclear magnetic resonance spectroscopy １ It can be obtained by performing 1H-NMR analysis and calculating from the results.

[0061] The thermoplastic resin composition of the present invention may consist of the above-mentioned thermoplastic resin, or it may consist of a thermoplastic resin and various additives.

[0062] Examples of additives include plasticizers, antioxidants, antioxidants, UV absorbers, transesterification inhibitors, fillers, flame retardants, anti-dripping agents, antistatic agents, lubricants, stabilizers, weather-resistant agents, water-repellent agents, oil-repellent agents, antibacterial agents, preservatives, and colorants.

[0063] Examples of plasticizers include phthalates, trimellitic acid esters, pyromellitic acid esters, aliphatic monobasic acid esters, aliphatic dibasic acid esters, phosphate esters, polyhydric alcohol esters, epoxy plasticizers, polymeric plasticizers, and chlorinated paraffins.

[0064] Examples of anti-aging agents include naphthylamine compounds, diphenylamine compounds, p-phenylenediamine compounds, quinoline compounds, hydroquinone derivative compounds, monophenol compounds, bisphenol compounds, trisphenol compounds, polyphenol compounds, thiobisphenol compounds, hinderedphenol compounds, phosphite ester compounds, imidazole compounds, nickel dithiocarbamate salt compounds, and phosphate compounds.

[0065] Examples of antioxidants include phosphite compounds, thioether compounds, hindered amine compounds, hydroquinone compounds, and hindered phenol compounds.

[0066] Examples of UV absorbers include benzophenone compounds, benzotriazole compounds, and triazine compounds.

[0067] Examples of phosphate compounds used as transesterification inhibitors include methyl phosphate, ethyl phosphate, isopropyl phosphate, butyl phosphate, lauryl phosphate, stearyl phosphate, dodecyl phosphate, octadecyl phosphate, behenyl phosphate, dimethyl phosphate, diethyl phosphate, diisopropyl phosphate, dibutyl phosphate, dilauryl phosphate, distearyl phosphate, didodecyl phosphate, dibehenyl phosphate, trimethyl phosphate, and triethyl phosphate.

[0068] Examples of fillers include heavy calcium carbonate, colloidal calcium carbonate, light calcium carbonate, magnesium carbonate, zinc carbonate, carbon black, clay, talc, fumed silica, calcined silica, precipitated silica, crushed silica, fused silica, kaolin, diatomaceous earth, zeolite, titanium dioxide, quicklime, iron oxide, zinc oxide, barium oxide, aluminum oxide, magnesium oxide, aluminum sulfate, glass fiber, carbon fiber, glass balloons, shirasu balloons, saran balloons, phenol balloons, and the like.

[0069] Examples of flame retardants include organophosphorus compounds, organohalogen compounds, silicone compounds, guanidine compounds, and inorganic compounds (such as aluminum hydroxide).

[0070] Examples of anti-dripping agents include (co)polymers containing structural units derived from tetrafluoroethylene, such as polytetrafluoroethylene and tetrafluoroethylene-hexafluoropropylene copolymers, as well as fluorine-containing compounds such as polyvinylidene fluoride and polyhexafluoropropylene. When anti-dripping agents are used in combination with flame retardants, flame retardancy may be improved.

[0071] Examples of antistatic agents include polymer-type antistatic agents, polyethylene glycol-type nonionic surfactants, polyhydric alcohol-type nonionic surfactants, anionic surfactants, cationic surfactants, amino acid-type amphoteric surfactants, and betaine-type amphoteric surfactants.

[0072] The thermoplastic resin composition of the present invention exhibits excellent moldability, making it suitable for the manufacture of molded articles by melting it. The melt mass flow rate (hereinafter also referred to as "MFR") in accordance with ISO 1133 is preferably 8 to 30 g / 10 min, more preferably 10 to 25 g / 10 min, under conditions of a temperature of 240°C and a load of 98 N.

[0073] The thermoplastic resin composition of the present invention can be manufactured by kneading the raw material components using an extruder, Banbury mixer, kneader, rolls, etc. During kneading, the raw material components may be kneaded all at once, or they may be kneaded using a multi-stage addition method. The kneading temperature is preferably 250°C or higher, more preferably 260°C to 280°C.

[0074] When manufacturing a thermoplastic resin composition containing additives such as colorants, the following methods can be applied: (1) A method in which only the thermoplastic resin is kneaded, and then the additive is added to the kneaded mixture and kneaded further. (2) A method in which the thermoplastic resin and additive are mixed together and kneaded. (3) A method in which the thermoplastic resin is divided and used, and a mixture consisting of a portion of the thermoplastic resin and the additive is kneaded together with the remaining thermoplastic resin.

[0075] The molded articles of the present invention can be manufactured by processing the thermoplastic resin composition of the present invention, or the raw material components that form its constituent components, using known molding equipment such as injection molding equipment, extrusion molding equipment, shape extrusion molding equipment, hollow molding equipment, compression molding equipment, vacuum molding equipment, foam molding equipment (including methods using supercritical fluid injection), blow molding equipment, injection compression molding equipment, gas-assisted molding equipment, water-assisted molding equipment, insulated mold molding equipment, rapid heating and cooling mold molding equipment, two-color molding equipment, sandwich molding equipment, and ultra-high-speed injection molding equipment. In other words, the molded articles of the present invention contain the thermoplastic resin composition of the present invention.

[0076] When manufacturing molded products using the above-described molding apparatus, the molding temperature and mold temperature are appropriately selected depending on the type of raw material components used. The cylinder temperature of the molding apparatus when manufacturing molded products is typically 250°C to 280°C. The mold temperature is typically 50°C to 80°C.

[0077] The molded article of the present invention contains Si elements derived from polycarbonate resin (A) and rubber polymer-reinforced vinyl resin (B). In the present invention, the Si element content is preferably 1.35% by mass or more, more preferably 1.40 to 10.00% by mass, and more preferably 1.40 to 5.0% by mass, from the viewpoint of the low-temperature impact resistance and weather resistance of the composition.

[0078] The molded article of the present invention may have through holes, grooves, recesses, protrusions, etc., at any position depending on the purpose, application, etc.

[0079] The molded articles of the present invention have a good molded appearance without gloss unevenness, regardless of the type of molding apparatus or molding method, and exhibit excellent low-temperature impact resistance and weather resistance. Regarding the low-temperature impact resistance of the molded articles, the Charpy impact strength at -30°C, measured under the conditions described below, is preferably 18 kJ / m². ２ More preferably 20 kJ / m ２ The above can be achieved. In addition, generally, when resin molded products are used in environments exposed to rain, wind, sunlight, electric lights, etc., defects may occur on their surface, etc. (such as a decrease in gloss or a change in color). However, with the molded products of the present invention, such defects are suppressed, and they have excellent weather resistance.

[0080] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples unless it exceeds the spirit of the invention. In the following, parts and percentages are by mass unless otherwise specified.

[0081] 1. Raw Materials The raw materials used in the manufacture of the thermoplastic resin composition are as follows:

[0082] 1-1. Thermoplastic Resins 1-1-1. Raw Materials (A) Polycarbonate-polydimethylsiloxane copolymer (A1) and polycarbonate resin (A2) were used as raw materials (A).

[0083] The following (A1-1), (A1-2), and (A1-3) were used as the polycarbonate-polydimethylsiloxane copolymer (A1).

[0084] As (A1-1), Idemitsu Kosan's polycarbonate-polydimethylsiloxane copolymer "TARFLON NEO AG1760" (product name) was used. The content ratios of part (a1) and part (a2) were 94% and 6%, respectively, and the MVR was 14 cm ３ The reaction time is 1.570 g / 10 min (300°C, 1.20 kg, ISO 1133). The refractive index at 23°C (wavelength 589 nm) is 1.570. For (A1-2), SAMYANG Corporation's polycarbonate-polydimethylsiloxane copolymer "TRIREX ST4-3022PJ" (trade name) was used. The content ratios of parts (a1) and (a2) were 94% and 6%, respectively, and the MFR was 4.0 g / 10 min (300°C, 2.16 kg, ASTM D 1238). The refractive index at 23°C (wavelength 589 nm) is 1.570. For (A1-3), SAMYANG Corporation's polycarbonate-polydimethylsiloxane copolymer "TRIREX ST6-3022PJ" (trade name) was used. The content ratios of parts (a1) and (a2) were 91% and 9%, respectively, and the MFR was 4.0 g / 10 min (300°C, 2.16 kg, ASTM D 1238). The refractive index at 23°C (wavelength 589 nm) was 1.569.

[0085] As the polycarbonate resin (A2), (A2-1) Mitsubishi Engineering Plastics' polycarbonate resin "NOVAREX 7022R" (product name) was used. MVR was 13 cm ３ The refractive index at 23°C (wavelength 589 nm) after 10 minutes (300°C, 1.20 kg, ISO 1133) is 1.586.

[0086] 1-1-2. Raw materials (B) Graft resin (B1) and graft resin (B2) were used as raw materials (B).

[0087] As the graft resin (B1), composite rubber-reinforced vinyl resins (B1-1) and (B1-2) obtained by the following synthesis method were used.

[0088] <Synthesis Method of B1-1> 98 parts of octamethylcyclotetrasiloxane and 2 parts of γ-methacryloyloxypropyldimethoxymethylsilane were mixed to obtain 100 parts of a siloxane mixture. To this mixture, an aqueous solution prepared by dissolving 0.67 parts of sodium dodecylbenzenesulfonate in 300 parts of deionized water was added and stirred in a homomixer, then passed through a homogenizer twice to obtain a stable pre-mixed organosiloxane latex. Next, 10 parts of dodecylbenzenesulfonic acid and 90 parts of deionized water were added to a reactor equipped with a condenser, jacket heater, and stirring device to prepare a 10% aqueous solution of dodecylbenzenesulfonic acid (acid catalyst aqueous solution). This acid catalyst aqueous solution was heated to 85°C, and while stirring, the pre-mixed organosiloxane latex was added dropwise over 2 hours to carry out a hydrolysis condensation reaction. After the end of the dropwise addition, the temperature was maintained for 3 hours, and then cooled to below 40°C. Next, the reaction product was neutralized to pH 7.0 with a 10% sodium hydroxide aqueous solution to obtain a latex containing polyorganosiloxane (b1-1) with a solid content of 18.0%. The volume-average particle size of the obtained polyorganosiloxane (b1-1) was measured using a particle size distribution analyzer "NanoTrac 150" (model name) manufactured by Nikkiso Co., Ltd., and was found to be 30 nm.

[0089] Furthermore, 200 parts of deionized water, 2 parts of potassium oleate, 4 parts of sodium dioctyl sulfosuccinate, 0.003 parts of ferrous sulfate heptahydrate, 0.009 parts of ethylenediaminetetraacetate disodium salt, and 0.3 parts of sodium formaldehyde sulfoxylate were charged into a reactor equipped with a condenser, jacket heater, and stirrer under a nitrogen stream and heated. When the temperature reached 60°C, a mixture consisting of 85 parts of n-butyl acrylate, 15 parts of methacrylic acid, and 0.5 parts of cumene hydroperoxide was continuously added dropwise over 120 minutes to polymerize them. After the dropwise addition was complete, the reaction solution was aged for another 2 hours while maintaining the temperature at 60°C to obtain a latex containing an acid group-containing copolymer with a polymerization conversion rate of 95% and a solid content of 30% (hereinafter referred to as "acid group-containing copolymer latex (b1-2)"). The volume-average particle size of the obtained acid group-containing copolymer was 120 nm.

[0090] Next, the latex containing 5.0 parts of polyorganosiloxane (b1-1), 0.6 parts of dipotassium alkenylsuccinate, and 190 parts of deionized water were charged into a reactor equipped with a condenser, jacket heater, and stirrer, and mixed. Subsequently, a mixture consisting of 45.0 parts of n-butyl acrylate, 0.6 parts of allyl methacrylate, 0.09 parts of 1,3-butylene glycol dimethacrylate, and 0.02 parts of t-butyl hydroperoxide, for forming polybutyl acrylate rubber, was added to the reactor. The atmosphere of the reactor was replaced with nitrogen by passing a nitrogen stream through it, and the raw material mixture was heated. When the temperature reached 60°C, an aqueous solution prepared by dissolving 0.000075 parts of ferrous sulfate heptahydrate, 0.00023 parts of ethylenediaminetetraacetate disodium salt, and 0.2 parts of sodium formaldehyde sulfoxylate in 10 parts of deionized water was added to initiate radical polymerization. After polymerization exothermic reaction was confirmed, the reaction system temperature was set to 75°C, and polymerization was continued until polymerization exothermic reaction was no longer detected. After polymerization exothermic reaction was no longer detected, this state was maintained for another hour to obtain a latex containing a composite rubber (F1) formed by the compounding of polyorganosiloxane and polybutyl acrylate rubber (radical polymerization step). The volume-average particle size of the obtained composite rubber (F1) was 90 nm. Subsequently, the reaction system temperature was lowered to 70°C, and an aqueous solution prepared by dissolving 0.20 parts of sodium pyrophosphate in water was added (condensate salt addition step). Next, with the temperature of the mixture set to 70°C, the above latex (b1-2) containing 0.26 parts of acid group-containing copolymer was added, and stirring was performed for 30 minutes to enlarge the composite rubber (F1) (enlargement step), obtaining a latex containing enlarged composite rubber (FF1). The volume-average particle size of the obtained enlarged composite rubber (FF1) was 150 nm, and the gel content was 95%.

[0091] Subsequently, an aqueous solution prepared by dissolving 0.001 parts ferrous sulfate heptahydrate, 0.003 parts ethylenediaminetetraacetate disodium salt, and 0.3 parts sodium formaldehyde sulfoxylate in 10 parts deionized water was added to a latex containing 50 parts of enlarged composite rubber (FF1) in solid content. Next, a mixture consisting of 8.8 parts acrylonitrile, 26.2 parts styrene, and 0.16 parts t-butyl hydroperoxide was added dropwise to the mixture, which was heated to 70°C, over 80 minutes to polymerize. The temperature of the reaction solution was maintained at 75°C for 30 minutes after the completion of the dropwise addition. Then, a mixture consisting of 3.8 parts acrylonitrile, 11.2 parts styrene, 0.07 parts t-butyl hydroperoxide, and 0.02 parts n-octyl mercaptan was added dropwise over 20 minutes to polymerize. The temperature of the reaction solution was maintained at 75°C for 30 minutes after the completion of the dropwise addition. Next, 0.05 parts of cumene hydroperoxide were added to the reaction solution, and the temperature of the reaction solution was maintained at 75°C for another 30 minutes. After that, it was cooled to obtain a latex containing the grafted composite rubber-reinforced vinyl resin (B1-1). The grafting rate of the composite rubber-reinforced vinyl resin (B1-1) was 50%, and the Mw determined by GPC was 14.6 × 10⁻⁶. ４ The composite rubber-reinforced vinyl resin (B1-1) used in the production of the thermoplastic resin composition was obtained by solidifying, washing, and drying the above-mentioned latex.

[0092] <Synthesis Method of B1-2> In a reactor equipped with a condenser, jacket heater, and stirring device, the above latex containing 6.0 parts of polyorganosiloxane (b1-1), 0.1 parts of sodium dodecylbenzenesulfonate, and 190 parts of deionized water were charged and mixed. Subsequently, a mixture consisting of 44.0 parts of n-butyl acrylate, 0.4 parts of allyl methacrylate, 0.09 parts of 1,3-butylene glycol dimethacrylate, and 0.12 parts of t-butyl hydroperoxide, for forming polybutyl acrylate rubber, was added to the reactor. The atmosphere of the reactor was replaced with nitrogen by passing a nitrogen stream through it, and the raw material mixture was heated. When the temperature reached 60°C, an aqueous solution prepared by dissolving 0.000075 parts of ferrous sulfate heptahydrate, 0.00023 parts of ethylenediaminetetraacetate disodium salt, and 0.2 parts of sodium formaldehyde sulfoxylate in 10 parts of deionized water was added to initiate radical polymerization. After polymerization exothermic reaction was confirmed, the temperature of the reaction system was raised to 75°C, and polymerization was continued until polymerization exothermic reaction was no longer detected. After polymerization exothermic reaction was no longer detected, this state was maintained for another hour to obtain a latex containing a composite rubber (F2) formed by the compounding of polyorganosiloxane and polybutyl acrylate-based rubber (radical polymerization step). The volume-average particle size of the obtained composite rubber (F2) was 90 nm.

[0093] Subsequently, an aqueous solution consisting of 0.2 parts sodium formaldehyde sulfoxylate and 10 parts deionized water was added to a latex containing 50 parts of composite rubber (F2) in solid content. Next, a mixture consisting of 2.5 parts acrylonitrile, 7.5 parts styrene, and 0.1 parts t-butyl hydroperoxide was added dropwise to the mixture, which was heated to 75°C, over 20 minutes to polymerize. The temperature of the reaction solution was maintained at 75°C for 30 minutes after the completion of the dropwise addition. Then, a mixture consisting of 10 parts acrylonitrile, 30 parts styrene, and 0.2 parts t-butyl hydroperoxide was added dropwise over 80 minutes to polymerize. The temperature of the reaction solution was maintained at 75°C for 30 minutes after the completion of the dropwise addition. Next, 0.05 parts cumene hydroperoxide was added to this reaction solution, and the temperature of the reaction solution was maintained at 75°C for another 30 minutes. Subsequently, the mixture was cooled to obtain a latex containing a composite rubber-reinforced vinyl resin (B1-2) as the graft material. The grafting rate of the composite rubber-reinforced vinyl resin (B1-2) was 81%, and the Mw was 14.5 × 10⁻⁶. ４ The composite rubber-reinforced vinyl resin (B1-2) used in the production of the thermoplastic resin composition was obtained by solidifying, washing, and drying the above-mentioned latex.

[0094] As the graft resin (B2), ASA resins (B2-1) and (B2-2) obtained by the following synthesis method were used.

[0095] <Synthesis Method of B2-1> In a reactor equipped with a condenser, jacket heater, and stirrer, 49.2 parts of n-butyl acrylate, 0.3 parts of allyl methacrylate, 0.5 parts of 1,3-butanediol dimethacrylate, 0.1 part of t-butyl hydroperoxide, 195 parts of deionized water, and 1.5 parts of dipotassium alkenylsuccinate were charged. After purging the reactor with nitrogen, the contents were heated. When the temperature reached 55°C, an aqueous solution prepared by dissolving 0.15 parts of sodium formaldehyde sulfoxylate, 0.0001 parts of ferrous sulfate heptahydrate, and 0.0002 parts of disodium ethylenediaminetetraacetate in 5 parts of deionized water was added to start polymerization. After polymerization exothermic reaction was confirmed, the temperature of the reaction system was raised to 75°C and polymerization was continued until polymerization exothermic reaction was no longer observed. After polymerization exothermic reaction was no longer observed, this state was maintained for another 30 minutes to obtain a latex containing polybutyl acrylate-based rubber polymer (b2-1). The volume-average particle size of this polybutyl acrylate-based rubber polymer (b2-1) was 85 nm.

[0096] Subsequently, an aqueous solution containing 0.2 parts sodium formaldehyde sulfoxylate dissolved in 10 parts deionized water was added to a latex containing 50 parts polybutyl acrylate rubber polymer (b2-1). Next, a mixture consisting of 2.5 parts acrylonitrile, 7.5 parts styrene, and 0.1 parts t-butyl hydroperoxide was added dropwise to this mixture, which was heated to 75°C, over 20 minutes to allow polymerization. The temperature of the reaction solution was maintained at 75°C for 30 minutes after the end of the dropwise addition. Then, a mixture consisting of 10 parts acrylonitrile, 30 parts styrene, and 0.2 parts t-butyl hydroperoxide was added dropwise to this reaction solution over 80 minutes to allow polymerization. The temperature of the reaction solution was maintained at 75°C for 30 minutes after the end of the dropwise addition. Next, 0.05 parts cumene hydroperoxide was added to this reaction solution, and the temperature of the reaction solution was maintained at 75°C for another 30 minutes. Subsequently, the material was cooled to obtain latex containing ASA resin (B2-1) as a graft material. The grafting rate of ASA resin (B2-1) was 70%, and the Mw was 14.4 × 10⁻⁶. ４ The ASA resin (B2-1) used in the production of the thermoplastic resin composition was obtained by solidifying, washing, and drying the above-mentioned latex.

[0097] <Synthesis Method of B2-2> 49.7 parts n-butyl acrylate, 1.0 part liquid paraffin, 0.3 parts allyl methacrylate, 0.05 parts 1,3-butanediol dimethacrylate, 0.3 parts dilauroyl peroxide, 200 parts deionized water, and 0.1 parts dipotassium alkenylsuccinate were charged into a container and stirred at room temperature at 9000 rpm for 5 minutes using an SMT Highflex Disperser HG92 (product name). The resulting mixture was treated twice using a Sanmaru Machinery Industry High-Pressure Homogenizer H3-1D (model name) at a pressure of 20 MPa and a flow rate of 135 L / hr to obtain preemulsion (e-1). Next, 50 parts of the obtained pre-emulsion (e-1) were charged into a reactor equipped with a condenser, jacket heater, and stirrer. After thoroughly purging the reactor with nitrogen, the contents were heated to 60°C while stirring, and radical polymerization was started. As polymerization progressed, the temperature of the reaction solution rose to 78°C. For the following 30 minutes, the temperature of the reaction solution was maintained at 75°C to complete the polymerization and obtain a latex containing a polybutyl acrylate-based rubber polymer (b2-2). The volume-average particle size of this polybutyl acrylate-based rubber polymer (b2-2) was 360 nm.

[0098] Subsequently, an aqueous solution prepared by dissolving 0.2 parts of sodium formaldehyde sulfoxylate in 10 parts of deionized water was added to a latex containing 50 parts of polybutyl acrylate-based rubber polymer (b2-2). Next, a mixture consisting of 2.5 parts of acrylonitrile, 7.5 parts of styrene, and 0.1 parts of t-butyl hydroperoxide was added dropwise to this mixture, which was heated to 75°C, over 20 minutes to allow polymerization. The temperature of the reaction solution was maintained at 75°C for 30 minutes after the end of the dropwise addition. Then, a mixture consisting of 10 parts of acrylonitrile, 30 parts of styrene, and 0.2 parts of t-butyl hydroperoxide was added dropwise to this reaction solution over 80 minutes to allow polymerization. The temperature of the reaction solution was maintained at 75°C for 30 minutes after the end of the dropwise addition. Next, 0.05 parts of cumene hydroperoxide was added to this reaction solution, and the temperature of the reaction solution was maintained at 75°C for another 30 minutes. Subsequently, the material was cooled to obtain a latex containing ASA resin (B2-2) as a graft material. The grafting rate of ASA resin (B2-2) was 40%, and the Mw was 15.8 × 10⁻⁶. ４ The ASA resin (B2-2) used in the production of the thermoplastic resin composition was obtained by solidifying, washing, and drying the above-mentioned latex.

[0099] 1-1-3. Raw materials (C) As raw materials (C), a vinyl resin (C1) containing structural units (c1) and (c2) and a vinyl resin (C2) not containing structural units (c1) and (c2) were used.

[0100] The following vinyl resins (C1), (C1-1), (C1-2), (C1-3), and (C1-4), were used as the vinyl resin (C1).

[0101] As (C1-1), a styrene-acrylonitrile copolymer consisting of 76% styrene units and 24% acrylonitrile units, obtained by a known suspension polymerization method, was used. Mw was 13.6 × 10⁻⁶ ４ As (C1-2), a styrene-acrylonitrile copolymer consisting of 80.5% by mass of styrene units and 19.5% by mass of acrylonitrile units, obtained by a known suspension polymerization method, was used. Mw was 18.0 × 10 ４As (C1-3), a copolymer consisting of 67.4% by mass of styrene units and 32.6% by mass of acrylonitrile units, obtained by a known suspension polymerization method, was used. Mw was 11.5 × 10 ４ As (C1-4), a copolymer consisting of 57.1% by mass of styrene units and 42.9% by mass of acrylonitrile units, obtained by a known suspension polymerization method, was used. Mw was 11.8 × 10⁻⁶. ４ That is the case.

[0102] As the vinyl resin (C2), (C2-1) Mitsubishi Chemical's polymethyl methacrylate "Acrypet VH5" (product name) was used. MFR was 5.5 g / 10 min (230°C, 3.8 kg, ISO 133), refractive index (n) at 23°C. Ｄ ) is 1.49 (ISO 89).

[0103] 1-1-4. Raw materials (D) Carbon black was used as a coloring agent.

[0104] 2. Production and Evaluation of Thermoplastic Resin Compositions Examples 1-12 and Comparative Examples 1-10 Raw materials (A) to (D) were blended in the proportions shown in Tables 1 and 2 and mixed using a Henschel mixer. This mixture was then supplied to a twin-screw extruder "SBTN32" (model name) manufactured by Plastics Engineering Research Institute Co., Ltd., with the cylinder set to 240°C, and melt-kneaded to obtain pellets made of a black-colored thermoplastic resin composition. Tables 1 and 2 show (a) the amount of Si measured by X-ray fluorescence analysis, (b) the absolute value of the refractive index difference between the corresponding raw materials (A) and (C) for the polycarbonate resin (A) and vinyl resin (C) according to the present invention, and (c) the content ratio of raw material (D) per 100 parts of thermoplastic resin.

[0105] The obtained thermoplastic resin compositions were subjected to the following various evaluation tests, and the results are shown in Tables 1 and 2.

[0106] (1) Low-temperature impact resistance: Using a Japan Steel Works injection molding machine "J110AD-180H" (model name), pellets made of a thermoplastic resin composition were subjected to injection molding (cylinder temperature 240°C) to obtain test specimens. The Charpy impact strength of these test specimens was then measured at -30°C according to the method specified in ISO 179-1.

[0107] (2) Pellets made of a weather-resistant thermoplastic resin composition were subjected to injection molding (cylinder temperature 240°C, mold temperature 60°C, injection rate 20 g / sec) to obtain a plate-shaped molded body (length 100 mm, width 100 mm, thickness 3 mm). Next, the degree of discoloration and surface gloss retention rate were measured using this plate-shaped molded body by the following method. <Degree of discoloration> Using an Atlas xenon weather meter "Ci4000" (model name) manufactured by Toyo Seiki Seisakusho, the plate-shaped molded body was subjected to irradiance: 0.50 W / m ２ The samples were exposed to a black panel under the following conditions: temperature 63°C, humidity 60% RH, and cycle conditions of 120 minutes (rainfall: 18 minutes). The color difference (ΔE) of the surface of the plate-shaped molded product after 1600 hours of exposure and the surface of the plate-shaped molded product before exposure was measured using a colorimeter. <Surface gloss retention rate> The reflectance (%) at an incident angle of 60° and a reflection angle of 60° was measured using a Suga Test Instruments Co., Ltd. digital angle-bending gloss meter "UGV-5D" (model name) in accordance with JIS K 7105 for the surface of the plate-shaped molded product after 1000 hours of exposure and the surface of the plate-shaped molded product before exposure, obtained using a Suga Test Instruments Co., Ltd. Sunshine Super Long Life Weather Meter "WEL-SUN-DCH" (model name). The gloss retention rate was calculated using the following formula: Gloss retention rate (%) = [(reflectance after exposure) / (reflectance before exposure)] × 100

[0108] (3) Fluidity The melt mass flow rate was measured at a temperature of 240°C and a load of 98N in accordance with ISO 1133.

[0109] (4) Appearance of molded products The presence or absence of gloss unevenness and the brightness L* measurement were performed on the surface of the plate-shaped molded products (immediately after manufacturing) used in the weather resistance evaluation above. <Gloss unevenness> The surface of the plate-shaped molded products was visually observed. ○: No pearlescent luster was observed at all. △: Pearlescent luster was observed in some areas. ×: Pearlescent luster was observed in large quantities over the entire surface. <Brightness L* measurement> Brightness L* was measured using the SCE method with a Konica Minolta Optips spectrophotometer "CM-3500d" (model name).

[0110]

[0111]

[0112] Tables 1 and 2 show that Examples 1 to 12 are examples of thermoplastic resin compositions having the structure of the present invention, exhibiting a good molded appearance without gloss unevenness, and demonstrating excellent low-temperature impact resistance and weather resistance.

[0113] Molded articles obtained using the thermoplastic resin composition of the present invention can be suitably used in both enclosed and outdoor environments where low temperatures may occur. For example, they are useful as interior components in vehicles, ships, aircraft, etc., as components (such as housings) in office automation equipment, household appliances, electrical and electronic equipment, building materials, etc., and as components in agricultural materials, daily necessities, sporting goods, stationery, etc.

Claims

1. A thermoplastic resin composition comprising (A) a polycarbonate resin, (B) a rubber polymer-reinforced vinyl resin obtained by polymerizing vinyl monomers in the presence of a rubber polymer, and (C) a vinyl resin (excluding the rubber polymer-reinforced vinyl resin (B)), wherein the polycarbonate resin (A) comprises a polycarbonate-polyorganosiloxane copolymer (A1) having a portion made of polycarbonate (a1) and a portion made of polyorganosiloxane (a2), and the rubber polymer-reinforced vinyl resin (B) comprises a graft resin (B1) obtained by polymerizing vinyl monomers in the presence of a composite rubber having a polymer portion (b1) containing structural units derived from an alkyl (meth)acrylate and a portion made of polyorganosiloxane (b2), The vinyl resin (C) contains structural units (c1) derived from an aromatic vinyl compound and structural units (c2) derived from a vinyl cyanide compound, wherein the content of the structural units (c2) is 18 to 40% by mass relative to the vinyl resin (C), and the total amount of each polyorganosiloxane derived from the polycarbonate / polyorganosiloxane copolymer (A1) and the graft resin (B1) relative to the total amount of the thermoplastic resin is 1.5 to 10.0% by mass, characterized in that the thermoplastic resin composition is characterized in that the vinyl resin (C) contains structural units (c1) derived from an aromatic vinyl compound and structural units (c2) derived from a vinyl cyanide compound, wherein the content of the structural units (c2) is 18 to 40% by mass relative to the vinyl resin (C), and the total amount of each polyorganosiloxane derived from the polycarbonate / polyorganosiloxane copolymer (A1) and the graft resin (B1) is 1.5 to 10.0% by mass.

2. The thermoplastic resin composition according to claim 1, wherein the content ratio of the composite rubber derived from the graft resin (B1) to the thermoplastic resin is 1.0 to 10.0% by mass.

3. The thermoplastic resin composition according to claim 1 or 2, wherein the volume-average particle diameter of the graft resin (B1) is 80 to 300 nm.

4. The thermoplastic resin composition according to any one of claims 1 to 3, wherein the absolute value of the difference between the refractive index of the polycarbonate resin (A) and the refractive index of the vinyl resin (C) is 0.05 or less.

5. The thermoplastic resin composition according to any one of claims 1 to 4, wherein the content ratios of the polycarbonate resin (A), the rubbery polymer-reinforced vinyl resin (B), and the vinyl resin (C) are 60 to 90% by mass, 3 to 20% by mass, and 3 to 30% by mass, respectively, when their total is 100% by mass.

6. The thermoplastic resin composition according to any one of claims 1 to 5, wherein the content of the portion (a2) consisting of polyorganosiloxane constituting the polycarbonate / polyorganosiloxane copolymer (A1) is 2 to 15% by mass relative to the polycarbonate resin (A).

7. The thermoplastic resin composition according to any one of claims 1 to 6, wherein the content of the portion (b2) consisting of polyorganosiloxane constituting the graft resin (B1) is 2 to 15% by mass relative to the rubbery polymer-reinforced vinyl resin (B).

8. A molded article characterized by comprising the thermoplastic resin composition described in any one of claims 1 to 7.

9. The molded article according to claim 8, wherein the content of Si element is 1.35% by mass or more.

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