Resin composition and molded article comprising same

Abstract

The present invention provides: a resin composition which exhibits excellent fluidity, resistance to wet heat and impact resistance and which undergoes little decrease in strength even if subjected to a wet heat treatment; and a molded article comprising same. This polycarbonate resin composition contains: (C) 0.5-6 parts by weight of an acrylic block copolymer (component C) containing a polymer block that contains an acrylic acid ester monomer unit and a polymer block containing a methacrylic acid ester monomer unit; and (D) 0.001-1 parts by weight of at least one type of compound (component D) selected from the group consisting of a phosphonic acid ester and a phosphate metal salt. (C) and (D) being contained relative to 100 parts by weight of a resin component comprising: (A) 40-90 parts by weight of a polycarbonate resin (component A); and (B) 10-60 parts by weight of a copolymer (component B) obtained by polymerizing an aromatic vinyl monomer and a vinyl cyanide monomer. The polycarbonate resin composition is characterized in that the content of the polymer block containing a methacrylic acid ester monomer unit in component C is 25 wt% or more of all blocks.

Description

Resin composition and molded article made from same

[0001] An object of the present invention is to provide a resin composition which is excellent in fluidity, moist heat resistance and impact resistance and which shows little loss in strength even after moist heat treatment, and a molded article made from the same.

[0002] Polycarbonate resins have excellent mechanical and thermal properties and are used in a variety of applications, primarily in the automotive, office automation, and electronic / electrical equipment fields. Furthermore, alloy resins obtained by blending polycarbonate resin with ABS resin or AS resin have been utilized in applications such as automotive parts, printer parts, personal computer housings, and computer parts, taking advantage of their excellent fluidity. In recent years, the use of alloy resins obtained by blending polycarbonate resin with ABS resin has increased, particularly in the automotive field. However, the incorporation of ABS resins can impair impact resistance. Therefore, efforts have been made to improve impact resistance. Patent Document 1 discloses a method of blending an impact modifier such as an acrylic graft copolymer with an alloy resin obtained by blending polycarbonate resin with ABS resin. Patent Document 2 discloses the addition of a phosphorus-based compound to an alloy resin obtained by blending polycarbonate resin with ABS resin. However, while these methods improve impact resistance, they do not improve moist heat resistance.

[0003] JP 2021-113287 A JP 2007-254507 A

[0004] An object of the present invention is to provide a resin composition which is excellent in fluidity, moist heat resistance and impact resistance and which shows little loss in strength even after moist heat treatment, and a molded article made from the same.

[0005] As a result of intensive research conducted by the present inventors in order to achieve the above-mentioned object, it was discovered that by adding an acrylic block copolymer containing polymer blocks containing acrylate ester monomer units and polymer blocks containing methacrylate ester monomer units, wherein the content of polymer blocks containing methacrylate ester monomer units is 25% by weight or more of all blocks, and at least one compound selected from the group consisting of phosphonate esters and phosphate metal salts, to a resin component comprising a polycarbonate resin and a copolymer obtained by polymerizing an aromatic vinyl monomer and a vinyl cyanide monomer, it is possible to provide a resin composition that is excellent in fluidity, moist heat resistance, and impact resistance and that exhibits little decrease in strength even after moist heat treatment, and a molded article made from the same, and this discovery led to the present invention.

[0006] That is, the present invention is as follows: 1. A polycarbonate resin composition comprising, relative to 100 parts by weight of a resin component consisting of (A) 40 to 90 parts by weight of a polycarbonate resin (component A), and (B) 10 to 60 parts by weight of a copolymer (component B) obtained by polymerizing an aromatic vinyl monomer and a vinyl cyanide monomer, (C) 0.5 to 6 parts by weight of an acrylic block copolymer (component C) containing a polymer block containing an acrylic acid ester monomer unit and a polymer block containing a methacrylic acid ester monomer unit, and (D) 0.001 to 1 part by weight of at least one compound (component D) selected from the group consisting of phosphonate esters and phosphate metal salts, wherein the content of polymer blocks containing methacrylic acid ester monomer units in component C is 25% by weight or more of all blocks. 2. The resin composition according to item 1 above, wherein component B is a copolymer produced by bulk polymerization without using a dispersant or emulsifier. 3. 3. The resin composition according to any one of items 1 to 3 above, wherein component D is at least one compound selected from the group consisting of triethylphosphonoacetate and stearyl acid phosphate zinc salt. 4. The resin composition according to any one of items 1 to 3 above, comprising 0.01 to 2.0 parts by weight of (E) a benzotriazole-based ultraviolet absorber (component E) per 100 parts by weight of the resin component. 5. A molded article made from the resin composition according to any one of items 1 to 4 above.

[0007] The resin composition of the present invention has excellent fluidity, moist heat resistance, and impact resistance, and is subject to little decrease in strength even after moist heat treatment. Therefore, the resin composition of the present invention can be suitably used as components in the automotive field, office automation equipment field, home appliances, and electrical and electronic fields, and is particularly suitable for automotive components, and the industrial effects it provides are exceptional.

[0008] The present invention will be further described in detail below.

[0009] (Component A: Polycarbonate Resin) The polycarbonate resin used in the present invention is obtained by reacting a dihydric phenol with a carbonate precursor. Examples of the reaction method include interfacial polymerization, melt transesterification, solid-phase transesterification of carbonate prepolymers, and ring-opening polymerization of cyclic carbonate compounds.

[0010] Representative examples of the dihydric phenol used herein include hydroquinone, resorcinol, 4,4'-biphenol, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane (commonly known as bisphenol A), 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxyphenyl)pentane, 4,4'-(p-phenylene) Examples of suitable dihydric phenols include 4,4'-(m-phenylenediisopropylidene)diphenol, 4,4'-(m-phenylenediisopropylidene)diphenol, 1,1-bis(4-hydroxyphenyl)-4-isopropylcyclohexane, bis(4-hydroxyphenyl)oxide, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)ketone, bis(4-hydroxyphenyl)ester, bis(4-hydroxy-3-methylphenyl)sulfide, 9,9-bis(4-hydroxyphenyl)fluorene, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene. Preferred dihydric phenols are bis(4-hydroxyphenyl)alkanes, and among these, bisphenol A is particularly preferred and widely used in terms of impact resistance.

[0011] In the present invention, in addition to bisphenol A-based polycarbonate resins, which are general-purpose polycarbonate resins, it is also possible to use special polycarbonate resins produced using other dihydric phenols as Component A. For example, polycarbonate resins (homopolymers or copolymers) using 4,4'-(m-phenylenediisopropylidene)diphenol (hereinafter sometimes abbreviated as "BPM"), 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as "Bis-TMC"), 9,9-bis(4-hydroxyphenyl)fluorene, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (hereinafter sometimes abbreviated as "BCF") as part or all of the dihydric phenol component are suitable for applications where dimensional change due to water absorption and dimensional stability are particularly strict requirements. These dihydric phenols other than BPA are preferably used in an amount of 5 mol % or more, particularly 10 mol % or more, of the total dihydric phenol components constituting the polycarbonate resin. In particular, when high rigidity and better moist heat resistance are required, it is particularly suitable that component A constituting the resin composition is a copolymer polycarbonate resin of the following (1) to (3).

[0012] (1) A copolymer polycarbonate resin in which, based on 100 mol% of the dihydric phenol component constituting the polycarbonate resin, BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, even more preferably 45 to 65 mol%) and BCF is 20 to 80 mol% (more preferably 25 to 60 mol%, even more preferably 35 to 55 mol%).

[0013] (2) A copolymer polycarbonate resin in which, based on 100 mol% of the dihydric phenol component constituting the polycarbonate resin, BPA accounts for 10 to 95 mol% (more preferably 50 to 90 mol%, even more preferably 60 to 85 mol%) and BCF accounts for 5 to 90 mol% (more preferably 10 to 50 mol%, even more preferably 15 to 40 mol%).

[0014] (3) A copolymer polycarbonate resin in which, based on 100 mol% of the dihydric phenol component constituting the polycarbonate resin, BPM accounts for 20 to 80 mol% (more preferably 40 to 75 mol%, even more preferably 45 to 65 mol%) and Bis-TMC accounts for 20 to 80 mol% (more preferably 25 to 60 mol%, even more preferably 35 to 55 mol%).

[0015] These special polycarbonate resins may be used alone or in a suitable mixture of two or more. They may also be used in a mixture with a commonly used bisphenol A polycarbonate resin. The production methods and properties of these special polycarbonate resins are described in detail in, for example, JP-A Nos. 6-172508, 8-27370, 2001-55435, and 2002-117580.

[0016] Among the various polycarbonate resins mentioned above, those having a water absorption rate and a glass transition temperature (Tg) within the following ranges by adjusting the copolymerization composition, etc., are particularly suitable in fields where dimensional stability is required, since the polymer itself has good resistance to moist heat and exhibits significantly reduced warpage after molding: (I) Polycarbonate resin having a water absorption rate of 0.05 to 0.15%, preferably 0.06 to 0.13%, and a Tg of 120 to 180°C, or (II) Polycarbonate resin having a Tg of 160 to 250°C, preferably 170 to 230°C, and a water absorption rate of 0.10 to 0.30%, preferably 0.13 to 0.30%, more preferably 0.14 to 0.27%.

[0017] Here, the water absorption rate of a polycarbonate resin is a value measured by using a disk-shaped test piece having a diameter of 45 mm and a thickness of 3.0 mm and immersing it in water at 23°C for 24 hours in accordance with ISO 62-1980, and measuring the moisture content after that. Also, Tg (glass transition temperature) is a value determined by differential scanning calorimetry (DSC) in accordance with JIS K7121.

[0018] Carbonate precursors that can be used include carbonyl halides, carbonic acid diesters, and haloformates, and specific examples include phosgene, diphenyl carbonate, and dihaloformates of dihydric phenols.

[0019] When producing a polycarbonate resin from the dihydric phenol and carbonate precursor by interfacial polymerization, a catalyst, a terminal stopper, an antioxidant to prevent oxidation of the dihydric phenol, etc. may be used as needed. The polycarbonate resin of the present invention also includes branched polycarbonate resins copolymerized with a trifunctional or higher polyfunctional aromatic compound, polyester carbonate resins copolymerized with an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid, copolymerized polycarbonate resins copolymerized with a bifunctional alcohol (including alicyclic), and polyester carbonate resins copolymerized with such bifunctional carboxylic acid and bifunctional alcohol. The resulting polycarbonate resins may also be a mixture of two or more of the resulting polycarbonate resins.

[0020] The branched polycarbonate resin can impart anti-drip properties to the resin composition of the present invention. Examples of the tri- or higher functional aromatic compound used in such a branched polycarbonate resin include phloroglucin, phloroglucside, 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-2,2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 4-[4-[1,1-bis(4- Examples of the 4-hydroxyphenyl ether include trisphenols such as {4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and acid chlorides thereof. Among these, 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred.

[0021] The structural units derived from polyfunctional aromatic compounds in the branched polycarbonate resin are preferably 0.01 to 1 mol%, more preferably 0.05 to 0.9 mol%, and even more preferably 0.05 to 0.8 mol%, based on the total 100 mol% of the structural units derived from dihydric phenols and the structural units derived from such polyfunctional aromatic compounds. Furthermore, particularly in the case of the melt transesterification method, branched structural units may be generated as a side reaction, and the amount of such branched structural units is preferably 0.001 to 1 mol%, more preferably 0.005 to 0.9 mol%, and even more preferably 0.01 to 0.8 mol%, based on the total 100 mol% of the structural units derived from dihydric phenols. The proportion of such branched structures is as follows: １ It can be calculated by H-NMR measurement.

[0022] The aliphatic difunctional carboxylic acid is preferably an α,ω-dicarboxylic acid. Preferred examples of the aliphatic difunctional carboxylic acid include straight-chain saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and icosane diacid, as well as alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. The difunctional alcohol is more preferably an alicyclic diol, such as cyclohexanedimethanol, cyclohexanediol, and tricyclodecanedimethanol.

[0023] The reaction modes of the methods for producing the polycarbonate resin of the present invention, such as interfacial polymerization, melt transesterification, carbonate prepolymer solid-phase transesterification, and ring-opening polymerization of a cyclic carbonate compound, are well known in various literatures and patent publications.

[0024] In producing the resin composition of the present invention, the viscosity average molecular weight (M) of the polycarbonate resin is not particularly limited, but is preferably 1.5×10 ４ ~4.0 x 10 ４ and more preferably 1.7 × 10 ４ ~3.5 x 10 ４ , and more preferably 1.9 × 10 ４ ~3.0 x 10 ４ The viscosity average molecular weight is 1.5 × 10 ４ On the other hand, polycarbonate resins having a viscosity average molecular weight of 4.0×10 may not be able to provide good mechanical properties. ４ Resin compositions obtained from polycarbonate resins exceeding this range are inferior in terms of fluidity during injection molding and therefore are inferior in versatility.

[0025] The polycarbonate resin may be a mixture of polycarbonate resins having a viscosity average molecular weight outside the above range. ４Polycarbonate resins having a viscosity average molecular weight exceeding 7×10 have improved entropy elasticity. As a result, they exhibit good molding processability in gas-assisted molding and foam molding, which are sometimes used when molding reinforced resin materials into structural members. Such improvement in molding processability is even better than that of the branched polycarbonate resins. In a more preferred embodiment, component A has a viscosity average molecular weight exceeding 7×10 ４ ~3 x 10 ５ Polycarbonate resin (A-1-1 component) and viscosity average molecular weight 1 × 10 ４ ~3 x 10 ４ and an aromatic polycarbonate resin (component A-1-2) having a viscosity average molecular weight of 1.6 × 10 ４ ~3.5 x 10 ４ A polycarbonate resin (component A-1) (hereinafter sometimes referred to as "polycarbonate resin containing a high molecular weight component") having the formula:

[0026] In the polycarbonate resin containing a high molecular weight component (component A-1), the molecular weight of component A-1-1 is 7×10 ４ ~2 x 10 ５ is preferable, and more preferably 8 × 10 ４ ~2 x 10 ５ , more preferably 1 × 10 ５ ~2 x 10 ５ , particularly preferably 1 × 10 ５ ~1.6 x 10 ５ The molecular weight of component A-1-2 is 1×10 ４ ~2.5 x 10 ４ is preferable, and more preferably 1.1 × 10 ４ ~2.4 x 10 ４ , and more preferably 1.2 × 10 ４ ~2.4 x 10 ４ , particularly preferably 1.2 × 10 ４ ~2.3 x 10 ４ is.

[0027] The high-molecular-weight component-containing polycarbonate resin (component A-1) can be obtained by mixing the components A-1-1 and A-1-2 in various ratios and adjusting the ratio to satisfy a predetermined molecular weight range. Preferably, the amount of component A-1-1 is 2 to 40% by weight, more preferably 3 to 30% by weight, even more preferably 4 to 20% by weight, and particularly preferably 5 to 20% by weight, based on 100% by weight of component A-1.

[0028] Examples of methods for preparing component A-1 include: (1) a method of independently polymerizing component A-1-1 and component A-1-2 and then mixing them; (2) a method of producing an aromatic polycarbonate resin that exhibits multiple polymer peaks in a molecular weight distribution chart obtained by GPC, in the same system, as typified by the method disclosed in JP-A-5-306336, and producing such an aromatic polycarbonate resin so as to satisfy the conditions for component A-1 of the present invention; and (3) a method of mixing an aromatic polycarbonate resin obtained by such a production method (production method (2)) with component A-1-1 and / or component A-1-2 that have been separately produced.

[0029] The viscosity average molecular weight in the present invention is determined by first calculating the specific viscosity (H ＳＰ ) was measured using an Ostwald viscometer from a solution of 0.7 g of polycarbonate resin dissolved in 100 ml of methylene chloride at 20°C, and the specific viscosity (H ＳＰ ) = (t - t ０ ) / t ０ [t ０ is the number of seconds for methylene chloride to fall, and t is the number of seconds for the sample solution to fall]. ＳＰ ) and calculate the viscosity average molecular weight M using the following formula: ＳＰ / c = [H] + 0.45 × [H] ２ c (where [H] is the intrinsic viscosity) [H] = 1.23 x 10 －４ M ０．８３ c=0.7

[0030] The viscosity average molecular weight of the polycarbonate resin in the resin composition of the present invention is calculated as follows: The composition is mixed with 20 to 30 times the weight of methylene chloride to dissolve the soluble components in the composition. The soluble components are collected by filtration through Celite. The solvent in the resulting solution is then removed. The solid obtained after solvent removal is thoroughly dried to obtain a solid of components soluble in methylene chloride. 0.7 g of this solid is dissolved in 100 ml of methylene chloride, and the specific viscosity at 20°C is determined in the same manner as above. The viscosity average molecular weight M is then calculated from the specific viscosity in the same manner as above.

[0031] The polycarbonate resin of the present invention may be a polycarbonate-polydiorganosiloxane copolymer resin, which is preferably prepared by copolymerizing a dihydric phenol represented by the following general formula (1) with a hydroxyaryl-terminated polydiorganosiloxane represented by the following general formula (3):

[0032]

[0033] [In the above general formula (1), R １ and R ２ each independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxy group; when there are multiple of each, they may be the same or different; e and f each represent an integer of 1 to 4; and W is a single bond or at least one group selected from the group consisting of groups represented by the following general formula (2):

[0034]

[0035] [In the above general formula (2), R １１ , R １２ , R１３ , R １４ , R １５ , R １６ , R １７ and R １８ each independently represents a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms; R １９ and R ２０ each independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxy group; when there are a plurality of groups, they may be the same or different; g is an integer from 1 to 10, and h is an integer from 4 to 7.

[0036]

[0037] [In the above general formula (3), R ３ , R ４ , R ５ , R ６ , R ７ and R ８ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and R ９ and R1 ０ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, p is a natural number, q is 0 or a natural number, and p+q is a natural number from 10 to 300. X is a divalent aliphatic group having 2 to 8 carbon atoms.

[0038] Examples of the dihydric phenol (I) represented by the general formula (1) include 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxy-3,3'-biphenyl)propane, 2,2- Bis(4-hydroxy-3-isopropylphenyl)propane, 2,2-bis(3-t-butyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, 2,2-bis(3-bromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)propane, 4,4'-dihydroxyphenyl)diphenylmethane, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 2,2'- Dimethyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 2,2'-diphenyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfide, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,Examples include 4-bis(4-hydroxyphenyl)cyclohexane, 1,3-bis(4-hydroxyphenyl)cyclohexane, 4,8-bis(4-hydroxyphenyl)tricyclo[5.2.1.02,6]decane, 4,4'-(1,3-adamantanediyl)diphenol, and 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane.

[0039] Among these, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-sulfonyldiphenol, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, and 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene are preferred, and 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane (BPZ), 4,4'-sulfonyldiphenol, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene are particularly preferred. Among these, 2,2-bis(4-hydroxyphenyl)propane is the most suitable due to its excellent strength and durability. These may be used alone or in combination of two or more.

[0040] As the hydroxyaryl-terminated polydiorganosiloxane represented by the above general formula (3), for example, the compounds shown below are preferably used.

[0041]

[0042] Hydroxyaryl-terminated polydiorganosiloxane (II) can be easily produced by subjecting a phenol having an olefinically unsaturated carbon-carbon bond, preferably vinylphenol, 2-allylphenol, isopropenylphenol, or 2-methoxy-4-allylphenol, to a hydrosilylation reaction at the end of a polysiloxane chain having a predetermined degree of polymerization. Among these, (2-allylphenol)-terminated polydiorganosiloxane and (2-methoxy-4-allylphenol)-terminated polydiorganosiloxane are preferred, with (2-allylphenol)-terminated polydimethylsiloxane and (2-methoxy-4-allylphenol)-terminated polydimethylsiloxane being particularly preferred. The hydroxyaryl-terminated polydiorganosiloxane (II) preferably has a molecular weight distribution (Mw / Mn) of 3 or less. To achieve even better low outgassing properties during high-temperature molding and low-temperature impact resistance, the molecular weight distribution (Mw / Mn) is more preferably 2.5 or less, and even more preferably 2 or less. If the upper limit of this preferred range is exceeded, the amount of outgassing during high-temperature molding may be large, and low-temperature impact resistance may be poor.

[0043] Furthermore, in order to achieve a high level of impact resistance, the diorganosiloxane degree of polymerization (p+q) of the hydroxyaryl-terminated polydiorganosiloxane (II) is suitably 10 to 300. The diorganosiloxane degree of polymerization (p+q) is preferably 10 to 200, more preferably 12 to 150, and even more preferably 14 to 100. Below the lower limit of this preferred range, the impact resistance that is a characteristic of polycarbonate-polydiorganosiloxane copolymers is not effectively exhibited, while above the upper limit of this preferred range, poor appearance appears.

[0044] The polydiorganosiloxane content of the polycarbonate-polydiorganosiloxane copolymer resin used in Component A is preferably 0.1 to 50% by weight. The polydiorganosiloxane content is more preferably 0.5 to 30% by weight, and even more preferably 1 to 20% by weight. At or above the lower limit of this preferred range, excellent impact resistance and flame retardancy are achieved, while at or below the upper limit of this preferred range, a stable appearance that is less susceptible to the effects of molding conditions is likely to be achieved. The polydiorganosiloxane polymerization degree and polydiorganosiloxane content are １ It can be calculated by H-NMR measurement.

[0045] In the present invention, the hydroxyaryl-terminated polydiorganosiloxane (II) may be used alone or in combination of two or more. Furthermore, other comonomers than the dihydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) may be used in an amount of up to 10% by weight based on the total weight of the copolymer, provided that the use of these comonomers does not interfere with the performance of the present invention.

[0046] In the present invention, a mixed solution containing an oligomer having terminal chloroformate groups is prepared in advance by reacting a dihydric phenol (I) with a carbonate-forming compound in a mixed solution of a water-insoluble organic solvent and an aqueous alkaline solution.

[0047] When producing an oligomer of dihydric phenol (I), the entire amount of dihydric phenol (I) used in the method of the present invention may be converted into an oligomer at once, or a portion of the oligomer may be added as a post-added monomer to the subsequent interfacial polycondensation reaction as a reaction raw material. The post-added monomer is added to rapidly advance the subsequent polycondensation reaction, and does not need to be added if not necessary. The method of this oligomer production reaction is not particularly limited, but is usually preferably carried out in a solvent in the presence of an acid binder.

[0048] The proportion of the carbonate ester-forming compound used may be appropriately adjusted taking into consideration the stoichiometric ratio (equivalents) of the reaction. When a gaseous carbonate ester-forming compound such as phosgene is used, it is preferable to employ a method in which the gaseous compound is blown into the reaction system.

[0049] Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof. Similarly, the proportion of the acid binder used may be determined appropriately in consideration of the stoichiometric ratio (equivalents) of the reaction. Specifically, it is preferable to use 2 equivalents or a slight excess of the acid binder relative to the number of moles of the dihydric phenol (I) used to form the oligomer (usually 1 mole corresponds to 2 equivalents).

[0050] The solvent may be any of various solvents inert to reactions, such as those used in the production of known polycarbonates, and may be used alone or in combination. Typical examples include hydrocarbon solvents such as xylene, and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. Halogenated hydrocarbon solvents such as methylene chloride are particularly preferred.

[0051] The reaction pressure for oligomer formation is not particularly limited and may be atmospheric, elevated, or reduced pressure, but it is usually advantageous to carry out the reaction under atmospheric pressure. The reaction temperature is selected from the range of -20 to 50°C, and since heat is often generated during polymerization, water or ice cooling is desirable. The reaction time depends on other conditions and cannot be specified in general, but is usually carried out for 0.2 to 10 hours. The pH range for the oligomer formation reaction is similar to that of known interfacial reaction conditions, and the pH is always adjusted to 10 or higher.

[0052] In the present invention, after obtaining a mixed solution containing an oligomer of dihydric phenol (I) having terminal chloroformate groups in this manner, the mixed solution is stirred while adding hydroxyaryl-terminated polydiorganosiloxane (II) represented by general formula (3), which has been highly purified to a molecular weight distribution (Mw / Mn) of 3 or less, to the dihydric phenol (I), and the hydroxyaryl-terminated polydiorganosiloxane (II) and the oligomer are subjected to interfacial polycondensation to obtain a polycarbonate-polydiorganosiloxane copolymer.

[0053]

[0054] [In the above general formula (3), R ３ , R ４ , R ５ , R ６ , R ７ and R ８ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and R ９ and R １０ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, p is a natural number, q is 0 or a natural number, and p+q is a natural number from 10 to 300. X is a divalent aliphatic group having 2 to 8 carbon atoms.

[0055] When carrying out the interfacial polycondensation reaction, an acid binder may be added as appropriate, taking into account the stoichiometric ratio (equivalent) of the reaction. Examples of acid binders include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof. Specifically, when the hydroxyaryl-terminated polydiorganosiloxane (II) used, or a portion of the dihydric phenol (I) as described above, is added to this reaction stage as a post-added monomer, it is preferable to use 2 equivalents or more of alkali relative to the total moles of the post-added dihydric phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II) (usually 1 mole corresponds to 2 equivalents).

[0056] The polycondensation by interfacial polycondensation reaction between the oligomer of dihydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) is carried out by vigorously stirring the mixture.

[0057] In such a polymerization reaction, a terminal terminator or a molecular weight modifier is usually used. Examples of the terminal terminator include compounds having a monovalent phenolic hydroxyl group, such as ordinary phenol, p-tert-butylphenol, p-cumylphenol, tribromophenol, etc., as well as long-chain alkylphenols, aliphatic carboxylic acid chlorides, aliphatic carboxylic acids, hydroxybenzoic acid alkyl esters, hydroxyphenyl alkyl acid esters, and alkyl ether phenols. The amount used is in the range of 100 to 0.5 mol, preferably 50 to 2 mol, per 100 mol of the total dihydric phenol compounds used. Naturally, two or more compounds can be used in combination.

[0058] To promote the polycondensation reaction, a catalyst such as a tertiary amine (e.g., triethylamine) or a quaternary ammonium salt may be added. The reaction time for such a polymerization reaction is preferably 30 minutes or more, more preferably 50 minutes or more. If desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfide may be added.

[0059] A branching agent can be used in combination with the above-mentioned dihydric phenol compound to produce a branched polycarbonate-polydiorganosiloxane. Examples of trifunctional or higher polyfunctional aromatic compounds used in such branched polycarbonate-polydiorganosiloxane copolymer resins include phloroglucin, phloroglucside, 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-2,2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 4-[4-[1 ,1-bis(4-hydroxyphenyl)ethyl]benzene}-α, α-dimethylbenzylphenol, trisphenols such as tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and acid chlorides thereof. Among these, 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred. The proportion of the polyfunctional compound in the branched polycarbonate-polydiorganosiloxane copolymer resin is preferably 0.001 to 1 mol %, more preferably 0.005 to 0.9 mol %, even more preferably 0.01 to 0.8 mol %, and particularly preferably 0.05 to 0.4 mol %, based on the total amount of the polycarbonate-polydiorganosiloxane copolymer resin. １ It can be calculated by H NMR measurement.

[0060] The reaction pressure can be reduced, normal, or increased, but is usually preferably normal pressure or the natural pressure of the reaction system. The reaction temperature is selected from the range of -20 to 50°C, and in many cases, water or ice cooling is desirable because heat is generated during polymerization. The reaction time cannot be generally specified because it varies depending on other conditions such as the reaction temperature, but is usually 0.5 to 10 hours.

[0061] Optionally, the obtained polycarbonate-polydiorganosiloxane copolymer resin may be subjected to a suitable physical treatment (mixing, fractionation, etc.) and / or chemical treatment (polymerization reaction, crosslinking treatment, partial decomposition treatment, etc.) to obtain a desired reduced viscosity [H ＳＰ / c] polycarbonate-polydiorganosiloxane copolymer resin.

[0062] The resulting reaction product (crude product) can be subjected to various post-treatments such as known separation and purification methods to recover a polycarbonate-polydiorganosiloxane copolymer resin of the desired purity (degree of purification).

[0063] The average size of the polydiorganosiloxane domains in the polycarbonate-polydiorganosiloxane copolymer resin molded article is preferably in the range of 1 to 60 nm. This average size is more preferably 3 to 55 nm, and even more preferably 5 to 50 nm. Below the lower limit of this preferred range, impact resistance and flame retardancy may not be sufficiently exhibited, while above the upper limit of this preferred range, impact resistance may not be stably exhibited.

[0064] (Component B: Copolymer Obtained by Polymerizing Aromatic Vinyl Monomer and Vinyl Cyanide Monomer) Component B of the present invention is a copolymer obtained by polymerizing an aromatic vinyl monomer and a vinyl cyanide monomer, and is preferably a copolymer obtained by polymerizing an aromatic vinyl monomer, a vinyl cyanide monomer, and a diene rubber polymer. Component B preferably comprises 40 to 90% by weight of aromatic vinyl monomer, 10 to 50% by weight of vinyl cyanide monomer, and 0 to 50% by weight of other polymers or monomers.

[0065] Examples of aromatic vinyl monomers include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, vinylxylene, ethylstyrene, dimethylstyrene, p-tert-butylstyrene, vinylnaphthalene, methoxystyrene, monobromostyrene, dibromostyrene, fluorostyrene, tribromostyrene, etc., with styrene being particularly preferred. The proportion of the aromatic vinyl monomer in Component B, relative to 100% by weight of Component B, is more preferably 45% by weight, even more preferably 50% by weight, and particularly preferably 55% by weight, and the upper limit is more preferably 75% by weight, even more preferably 70% by weight, and particularly preferably 65% ​​by weight.

[0066] Examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile, with acrylonitrile being particularly preferred. The proportion of the vinyl cyanide monomer in Component B, based on 100% by weight of Component B, is preferably 12% by weight at the lower end, more preferably 14% by weight at the lower end, and particularly preferably 15% by weight at the upper end, and more preferably 28% by weight at the upper end, more preferably 26% by weight at the upper end, and particularly preferably 25% by weight at the upper end.

[0067] Furthermore, copolymers of other polymers or monomers copolymerizable with these may also be used, and in this case, examples of the copolymerizable polymer include diene-based rubber polymers using rubber components such as polybutadiene, polyisoprene, and styrene-butadiene copolymers, and examples of the other copolymerizable monomers include monomers other than (meth)acrylic acid ester compounds, for example, maleimide-based monomers such as maleimide, N-methylmaleimide, N-cyclohexylmaleimide, and N-phenylmaleimide, acrylamide-based monomers such as acrylamide and N-methylacrylamide, unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride, and unsaturated acids such as acrylic acid and methacrylic acid. The upper limit of the proportion of other monomers in Component B, based on 100% by weight of Component B, is more preferably 40% by weight, and even more preferably 30% by weight.

[0068] Specific preferred examples of component B include acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-butadiene-styrene-α-methylstyrene copolymer, acrylonitrile-butadiene-styrene-N-phenylmaleimide copolymer, etc., and among these, acrylonitrile-butadiene-styrene copolymer is preferred. These copolymers may be used alone or in combination of two or more.

[0069] Component B is preferably produced by bulk polymerization without using a dispersant or an emulsifier, and the copolymerization method may be either a single-stage graft or a multi-stage graft. It may also be a mixture with a copolymer of only the graft component produced as a by-product during production.

[0070] The content of Component B is 10 to 60 parts by weight, preferably 15 to 50 parts by weight, and more preferably 20 to 45 parts by weight, per 100 parts by weight of the resin component. If the content of Component B is less than 10 parts by weight, sufficient fluidity cannot be obtained, and if it exceeds 60 parts by weight, moist heat resistance and impact resistance deteriorate.

[0071] (Component C: Acrylic Block Copolymer) The acrylic block copolymer used in the present invention is an acrylic block copolymer containing a polymer block containing an acrylic acid ester monomer unit and a polymer block containing a methacrylic acid ester monomer unit, and the content of the polymer block containing the methacrylic acid ester monomer unit in all blocks is 25% by weight or more. The content is preferably 35% by weight or more, and more preferably 45% by weight or more. If the content is less than 25% by weight, impact resistance decreases. The upper limit of the content is not particularly limited, but it is preferably 60% by weight or less.

[0072] Examples of the acrylic acid ester monomer include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, phenyl acrylate, and dimethylaminoethyl acrylate.

[0073] Examples of the methacrylic acid ester monomer include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, nonyl methacrylate, octadecyl methacrylate, dodecyl methacrylate, and 2-ethylhexyl methacrylate.

[0074] The content of component C is 0.5 to 6 parts by weight, preferably 0.8 to 5 parts by weight, and more preferably 1 to 4 parts by weight, per 100 parts by weight of the resin component consisting of components A and B. When the content of component C is less than 0.5 part by weight or exceeds 6 parts by weight, the impact resistance deteriorates.

[0075] <Component D: At least one compound selected from the group consisting of phosphonate esters and phosphate metal salts> The phosphonate ester used in the present invention can be a phosphonate monoester, phosphonate diester, or phosphonate triester, with phosphonate triesters being preferred. Various combinations of esters with carbon atoms ranging from 1 to 22 can be used, with triethyl phosphonoacetate being most preferred. The phosphate metal salt used in the present invention can be produced by a dry process involving the direct reaction of a fatty acid with a metal oxide or a fatty acid with a metal hydroxide, or by a wet process involving the reaction of a fatty acid sodium salt with a metal salt in an aqueous solution. Various combinations of fatty acids with carbon atoms ranging from 1 to 22 can be used, with those with 18 carbon atoms being more preferred. The phosphate metal salt is most preferably stearyl acid phosphate zinc salt. If Component D is a phosphorus-based antioxidant other than at least one compound selected from the group consisting of phosphonate esters and phosphate metal salts, the moist heat resistance and impact resistance after moist heat treatment will be impaired.

[0076] The content of component D is 0.001 to 1 part by weight, preferably 0.02 to 0.15 parts by weight, and more preferably 0.04 to 0.1 part by weight, per 100 parts by weight of the resin component consisting of components A and B. When the content of component D is less than 0.001 part by weight or more than 1 part by weight, the moist heat resistance and the impact resistance after moist heat treatment deteriorate.

[0077] <Component E: Benzotriazole-Based UV Absorber> Examples of benzotriazole-based UV absorbers include 2-(2-hydroxy-5-methylphenyl)2H-benzotriazole, 2-(2-hydroxy-5-t-octylphenyl)benzotriazole, 2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-chloro-2H-benzotriazole, 2-(3,5-di-t-pentyl-2-hydroxyphenyl)-2H-benzotriazole, and 2-(2H-benzotriazol-2-yl)-4-methyl-6-(3,4,5,6-tetrahydrophthalimidylmethyl)phenol. 2-(2-hydroxy-4-octyloxyphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-t-octylphenyl)-2H-benzotriazole, 2-[2'-hydroxy-3,5-di(1,1-dimethylbenzyl)phenyl]-2H-benzotriazole, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)4-(1,1,3,3-tetramethylbutyl)phenol], etc. Among these, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, etc. is preferred, and a specific example is Tinuvin 234 manufactured by BASF.

[0078] The content of component E is preferably 0.01 to 2.0 parts by weight, more preferably 0.02 to 1.5 parts by weight, and even more preferably 0.03 to 1.0 part by weight, per 100 parts by weight of the resin component consisting of components A and B.

[0079] (Other Additives) (I) Phosphorus-Based Antioxidant The resin composition of the present invention may contain, in addition to Component D, a phosphorus-based antioxidant other than Component D, within the range that does not impair the effects of the present invention.

[0080] The phosphorus-based antioxidant is not particularly limited, and examples thereof include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof, excluding component D, as well as tertiary phosphines. These phosphorus-based antioxidants can be used alone or in combination of two or more. Examples of phosphite compounds include trialkyl phosphites such as tridecyl phosphite, dialkyl monoaryl phosphites such as didecyl monophenyl phosphite, monoalkyl diaryl phosphites such as monobutyl diphenyl phosphite, triaryl phosphites such as triphenyl phosphite and tris(2,4-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol, and the like. Examples of the phosphate compound include pentaerythritol phosphites such as 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite and 2,2'-methylenebis(4,6-di-tert-butylphenyl)(2,4-di-tert-butylphenyl)phosphite. Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, and diisopropyl phosphate, with triphenyl phosphate and trimethyl phosphate being preferred. Preferred examples of the phosphonite compound include tetrakis(di-tert-butylphenyl)-biphenylene diphosphonite and bis(di-tert-butylphenyl)-phenyl-phenyl phosphonite, and more preferred are tetrakis(2,4-di-tert-butylphenyl)-biphenylene diphosphonite and bis(2,4-di-tert-butylphenyl)-phenyl-phenyl phosphonite.Such phosphonite compounds can be used in combination with the above-mentioned phosphite compounds having an aryl group substituted with two or more alkyl groups, and are preferred. Examples of phosphonate compounds include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate. Examples of tertiary phosphines include triphenylphosphine.

[0081] The content of the phosphorus-based antioxidant other than component D is preferably 0.01 to 3.0 parts by weight, more preferably 0.05 to 2.0 parts by weight, and even more preferably 0.1 to 1.0 part by weight, per 100 parts by weight of the resin component.

[0082] (II) Hindered Phenol-Based Antioxidant The hindered phenol-based antioxidant used in the present invention is not particularly limited, and various compounds that are usually blended into resins can be used. Examples of such hindered phenol-based antioxidants include α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, 2,6-di-tert-butyl-4-(N,N-dimethylaminomethyl)phenol, 3,5-di-tert-butyl ethyl-4-hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-methylenebis(2,6-di-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-dimethylene-bis(6-α-methyl-benzyl-p-cresol), 2,2'-ethylidene-bis(4,6-di-tert- butylphenol), 2,2'-butylidene-bis(4-methyl-6-tert-butylphenol), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], bis[2-tert-butyl-4-methyl-6-(3-tert-butyl- 5-methyl-2-hydroxybenzyl)phenyl] terephthalate, 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, 4,4'-thiobis(6-tert-butyl-m-cresol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-thiobis(4-methyl-6-tert-butylphenol), bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4'-di-thiobis(2,6-di-tert-butylphenol), 4,4'-tri-thiobis(2,6-di-tert-butylphenol), 2,2-thiodiethylenebis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine, N,N'-hexamethylenebis-(3,5- di-tert-butyl-4-hydroxyhydrocinnamide), N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-tert-butyl-4-hydroxyphenyl)isocyanurate, tris(3,5-di-tert-butyl 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 1,3,5-tris-2[3(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl isocyanurate, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methyl phenyl)propionate, triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)acetate, 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)acetyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, tetrakis[methylene-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]methane, 1,3,5-trimethyl-2,4,Examples include 6-tris(3-tert-butyl-4-hydroxy-5-methylbenzyl)benzene and tris(3-tert-butyl-4-hydroxy-5-methylbenzyl)isocyanurate. Among the above compounds, tetrakis[methylene-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]methane, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and 3,9-bis[2-{3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane are preferably used in the present invention. Particularly preferred is 3,9-bis[2-{3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane.

[0083] The above hindered phenol-based antioxidants can be used alone or in combination of two or more. The content of the hindered phenol-based antioxidant is preferably 0.05 to 1.0 part by weight, more preferably 0.07 to 0.8 parts by weight, and even more preferably 0.1 to 0.5 parts by weight, per 100 parts by weight of the resin component. If the content is less than 0.05 part by weight, the effect of suppressing thermal decomposition during processing will not be exerted, and mechanical properties may deteriorate. However, if the content exceeds 1.0 part by weight, mechanical properties may deteriorate.

[0084] It is preferable to use either a phosphorus-based antioxidant or a hindered phenol-based antioxidant, and more preferably to use them in combination. When using them in combination, it is preferable to use 0.01 to 0.5 parts by weight of the phosphorus-based antioxidant and 0.01 to 0.5 parts by weight of the hindered phenol-based antioxidant per 100 parts by weight of the resin component.

[0085] (III) Heat Stabilizers Other Than Phosphorus-Based and Hindered Phenol-Based Antioxidants The resin composition of the present invention can contain heat stabilizers other than the above-mentioned phosphorus-based and hindered phenol-based antioxidants. Such heat stabilizers are preferably used in combination with these antioxidants, and particularly preferably in combination with both. Suitable examples of such other heat stabilizers include lactone-based stabilizers, such as the reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene (details of such stabilizers are described in JP-A-7-233160). Such compounds are commercially available under the trade name Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS), and this compound can be used. Furthermore, stabilizers containing this compound in combination with various phosphite compounds and hindered phenol compounds are commercially available. A suitable example is Irganox HP-2921 manufactured by the same company. In the present invention, such premixed stabilizers can also be used. The amount of the lactone stabilizer to be added is preferably 0.0005 to 0.05 parts by weight, more preferably 0.001 to 0.03 parts by weight, per 100 parts by weight of the resin component.

[0086] Other examples of stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. Such stabilizers are particularly effective when the resin composition is used for rotational molding. The amount of such sulfur-containing stabilizers is preferably 0.001 to 0.1 parts by weight, more preferably 0.01 to 0.08 parts by weight, per 100 parts by weight of the resin component.

[0087] (IV) Mold Release Agents The resin composition of the present invention can be blended with a mold release agent to improve productivity during molding and reduce distortion of molded products, provided the effects of the present invention are not impaired. Known mold release agents can be used. Examples include saturated fatty acid esters, unsaturated fatty acid esters, silicone compounds, fluorine compounds (such as fluorinated oils typified by polyfluoroalkyl ethers), paraffin wax, and beeswax. Fatty acid esters are preferred mold release agents. Fatty acid esters are esters of aliphatic alcohols and aliphatic carboxylic acids. The aliphatic alcohols may be monohydric or polyhydric alcohols (dihydric or higher). The carbon number of the alcohol is in the range of 3 to 32, more preferably 5 to 30. Examples of such monohydric alcohols include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, ceryl alcohol, and triacontanol. Examples of such polyhydric alcohols include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerols (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol. Polyhydric alcohols are more preferred for the fatty acid esters of the present invention. On the other hand, the aliphatic carboxylic acid preferably has 3 to 32 carbon atoms, and particularly preferably has 10 to 22 carbon atoms. Examples of such aliphatic carboxylic acids include saturated aliphatic carboxylic acids such as decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, behenic acid, icosanoic acid, and docosanoic acid, as well as unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and cetoleic acid. Among the above, the aliphatic carboxylic acids are preferably those having 14 to 20 carbon atoms. Among these, saturated aliphatic carboxylic acids are more preferred. Stearic acid and palmitic acid are particularly preferred.The above-mentioned aliphatic carboxylic acids, such as stearic acid and palmitic acid, are typically produced from natural oils and fats, such as animal oils and fats (e.g., beef tallow and lard) and vegetable oils and fats (e.g., palm oil and sunflower oil). Therefore, these aliphatic carboxylic acids are typically mixtures containing other carboxylic acid components with different numbers of carbon atoms. Therefore, in the production of the fatty acid esters of the present invention, aliphatic carboxylic acids produced from such natural oils and fats and in the form of mixtures containing other carboxylic acid components, particularly stearic acid and palmitic acid, are preferably used. The fatty acid esters may be either partial esters or full esters (full esters). However, partial esters typically have a high hydroxyl value, which can easily induce resin decomposition at high temperatures. Therefore, full esters are more preferred. From the viewpoint of thermal stability, the acid value of the fatty acid esters of the present invention is preferably 20 or less, more preferably in the range of 4 to 20, and even more preferably in the range of 4 to 12. The acid value can be substantially zero. The hydroxyl value of the fatty acid esters is more preferably in the range of 0.1 to 30. The iodine value is preferably 10 or less. The iodine value can be substantially zero. These properties can be determined by the method specified in JIS K 0070.

[0088] The content of the release agent is preferably 0.01 to 4.0 parts by weight, more preferably 0.05 to 3.0 parts by weight, and even more preferably 0.1 to 2.5 parts by weight, based on 100 parts by weight of the resin component.

[0089] (V) Other Resins The resin composition of the present invention may contain other resins in small proportions as long as the effects of the present invention are exhibited. Examples of such other resins include polypropylene resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyamide resin, polyimide resin, polyetherimide resin, polyurethane resin, silicone resin, polyphenylene ether resin, polyphenylene sulfide resin, polysulfone resin, polymethacrylate resin, phenolic resin, and fluororesin.

[0090] (VI) Dyes and Pigments The resin composition of the present invention can further contain various dyes and pigments, thereby providing molded articles with a variety of designs. By blending a fluorescent whitening agent or other fluorescent dye that emits light, it is possible to impart even better design effects by taking advantage of the emitted color. It is also possible to provide resin compositions that are colored with extremely small amounts of dyes and pigments and have vivid color development.

[0091] Examples of fluorescent dyes (including fluorescent brighteners) used in the present invention include coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, perylene-based fluorescent dyes, anthraquinone-based fluorescent dyes, thioindigo-based fluorescent dyes, xanthene-based fluorescent dyes, xanthone-based fluorescent dyes, thioxanthene-based fluorescent dyes, thioxanthone-based fluorescent dyes, thiazine-based fluorescent dyes, and diaminostilbene-based fluorescent dyes. Among these, coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, and perylene-based fluorescent dyes are preferred because they have good heat resistance and are less susceptible to deterioration during molding and processing of polycarbonate resins.

[0092] Examples of dyes other than the bluing agents and fluorescent dyes include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as Prussian blue, perinone dyes, quinoline dyes, quinacridone dyes, dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Furthermore, the resin composition of the present invention can be blended with a metallic pigment to obtain a better metallic color. Suitable metallic pigments include those having a metal coating or a metal oxide coating on various plate-like fillers.

[0093] The content of the dye or pigment is preferably 0.00001 to 1 part by weight, and more preferably 0.00005 to 0.5 parts by weight, per 100 parts by weight of the resin component.

[0094] (VII) Flame Retardant The resin composition of the present invention can be applied with various compounds conventionally known as flame retardants for thermoplastic resins, particularly polycarbonate resins, but more preferably (I) halogen-based flame retardants (such as brominated polycarbonate compounds), (II) phosphorus-based flame retardants (such as monophosphate compounds, phosphate oligomer compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, phosphonic acid amide compounds, and phosphazene compounds), (III) metal salt-based flame retardants (such as organic sulfonic acid alkali (earth) metal salts, boric acid metal salt-based flame retardants, and stannic acid metal salt-based flame retardants), and (IV) silicone-based flame retardants made of silicone compounds.The incorporation of the compounds used as flame retardants not only improves flame retardancy, but also, depending on the properties of each compound, improves, for example, antistatic properties, fluidity, rigidity, and thermal stability.

[0095] The content of the flame retardant is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 28 parts by weight, and even more preferably 0.08 to 25 parts by weight, relative to 100 parts by weight of the resin component. If the content of the flame retardant is less than 0.01 part by weight, sufficient flame retardancy may not be obtained, whereas if it exceeds 30 parts by weight, mechanical properties may be significantly reduced.

[0096] (VIII) Highly Light-Reflecting White Pigment The resin composition of the present invention can be blended with a highly light-reflecting white pigment to impart a light-reflecting effect. Examples of such white pigments include zinc sulfide, zinc oxide, barium sulfate, calcium carbonate, and calcined kaolin. The content of such highly light-reflecting white pigment is preferably 1 to 30 parts by weight, more preferably 3 to 25 parts by weight, per 100 parts by weight of the resin component. Two or more types of highly light-reflecting white pigments can be used in combination.

[0097] (IX) Carbon Black The resin composition of the present invention can be colored by blending carbon black. The raw material type and production method of the carbon black are not limited, and any conventionally known carbon black can be used. For example, acetylene black, ketjen black, channel black, oil furnace black, etc. can be used. Furthermore, there are no limitations on the average particle size, structure, or surface properties, and commercially available carbon black can be appropriately selected and used.

[0098] In the resin composition of the present invention, carbon black is preferably added as a masterbatch with a styrene-based resin, and the styrene-based resin is preferably a polystyrene resin or an acrylonitrile-styrene resin. The masterbatch may also contain components other than the carbon black and the styrene-based resin. While the method for producing the masterbatch is not particularly limited, a method in which components containing carbon black and the styrene-based resin are kneaded using an extruder is preferred. The carbon black content in the masterbatch is preferably 20 to 60 parts by weight, more preferably 30 to 55 parts by weight, per 100 parts by weight of the masterbatch. The carbon black content is preferably 0.01 to 3 parts by weight, more preferably 0.05 to 2.5 parts by weight, and even more preferably 0.1 to 2 parts by weight, per 100 parts by weight of the resin component consisting of component A and component B.

[0099] (X) Other Additives: The resin composition of the present invention may contain small amounts of known additives to impart various functions to molded articles or improve their properties. These additives may be added in conventional amounts as long as they do not impair the objectives of the present invention. Examples of such additives include anti-fouling agents (e.g., PTFE particles), light diffusing agents (e.g., acrylic cross-linked particles, silicon cross-linked particles, ultrathin glass flakes, calcium carbonate particles), inorganic phosphors (e.g., phosphors with aluminate as the host crystal), antistatic agents, crystal nucleating agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents (e.g., titanium dioxide microparticles, zinc oxide microparticles), radical generators, infrared absorbers (heat ray absorbers), and photochromic agents.

[0100] (Method for Preparing Resin Composition) The resin composition of the present invention is preferably prepared by mixing the above components simultaneously or in any order using a mixer such as a tumbler, V-type blender, Nauta mixer, Banbury mixer, kneading roll, or extruder. As a mixer, melt kneading using a twin-screw extruder is preferred. If necessary, any component is preferably fed into the other melt-mixed components through a second feed port using a side feeder or the like. The extruded resin as described above is either directly cut and pelletized, or formed into strands, which are then cut and pelletized using a pelletizer. If it is necessary to reduce the influence of external dust during pelletization, it is preferable to purify the atmosphere around the extruder. The resulting pellets can have common shapes such as cylinders, prisms, and spheres, but cylinders are more preferred. The diameter of the cylinders is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and even more preferably 2 to 3.5 mm. The length of the cylinders is preferably 1 to 30 mm, more preferably 2 to 5 mm, and even more preferably 2.5 to 4 mm.

[0101] (Regarding Molded Articles Made from the Resin Composition of the Present Invention) The resin composition of the present invention can be used to produce various products by injection molding pellets obtained by the above-described method. In such injection molding, molded articles can be obtained using not only conventional molding methods but also injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including injection of supercritical fluids), insert molding, in-mold coating molding, heat-insulating mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding, and ultra-high-speed injection molding, depending on the purpose. The advantages of these various molding methods are already widely known. Furthermore, molding can be performed using either a cold runner system or a hot runner system.

[0102] The present invention will be described in more detail below with reference to examples. In the following, "parts" means "parts by weight" and "%" means "% by weight" unless otherwise specified.

[0103] (1) Preparation of Resin Composition (1-1) Raw Materials Used (Component A) A-1: ​​Polycarbonate resin powder with a molecular weight of 23,900 obtained by the following method. A baffled reaction vessel was equipped with a three-stage, six-blade agitator and a reflux condenser. This reaction vessel was charged with 45.6 parts of bisphenol A, 2.78 mol% of p-tert-butylphenol relative to bisphenol A, 265 parts of dichloromethane, and 200 parts of water, and nitrogen purging was performed to remove oxygen from the reaction vessel. At this stage, the contents of the reaction vessel were slightly less than 80% of the vessel's capacity. Next, approximately 80 parts of an aqueous solution containing 0.09 parts of sodium hydrosulfite and 21.8 parts of sodium hydroxide were added to the suspension, and bisphenol A was dissolved at 15°C. With stirring, 23.35 parts of phosgene was added to this mixture over 30 minutes. Thereafter, 0.016 parts of triethylamine (0.08 mol % relative to bisphenol A) was added, and the mixture was stirred for 60 minutes to terminate the reaction. The reaction mixture was then allowed to stand, and the organic phase was separated. Methylene chloride was added to the resulting dichloromethane solution of polycarbonate resin to give a solution with a concentration of 14% by weight. This solution was then treated using a perforated plate centrifugal extractor (KCC centrifugal extractor, manufactured by Kawasaki Engineering Co., Ltd.) with 0.5% aqueous sodium hydroxide at a flow rate of 1,000 ml / min and the organic phase at a flow rate of 1,000 ml / min at 3,500 rpm. The organic phase was then acidified with hydrochloric acid, and then repeatedly washed with water. When the conductivity of the aqueous phase became nearly the same as that of ion-exchanged water, the methylene chloride was evaporated to obtain a polycarbonate resin powder.

[0104] (Component B) B-1: ABS resin (MAGNUM A371 (trade name) manufactured by TRINSEO S.A.; produced by bulk polymerization without using a dispersant or emulsifier) ​​B-2: ABS resin (MAGNUM A156 (trade name) manufactured by TRINSEO S.A.; produced by bulk polymerization without using a dispersant or emulsifier)

[0105] (Component C) C-1: Acrylic block copolymer containing a polymer block containing an acrylic ester monomer unit and a polymer block containing a methacrylic ester monomer unit (content of polymer blocks containing methacrylic ester monomer units in the acrylic block copolymer: 50% by weight, Kuraray Co., Ltd., Kuraity LA4285) C-2: Acrylic block copolymer containing a polymer block containing an acrylic ester monomer unit and a polymer block containing a methacrylic ester monomer unit (content of polymer blocks containing methacrylic ester monomer units in the acrylic block copolymer: 40% by weight, Kuraray Co., Ltd., Kuraity LA2270) C-3: Acrylic block copolymer containing a polymer block containing an acrylic ester monomer unit and a polymer block containing a methacrylic ester monomer unit (content of polymer blocks containing methacrylic ester monomer units in the acrylic block copolymer: 30% by weight, Kuraray Co., Ltd., Kuraity LA2250) C-4 (Comparative Example): Acrylic block copolymer containing a polymer block containing an acrylic acid ester monomer unit and a polymer block containing a methacrylic acid ester monomer unit (content of polymer block containing a methacrylic acid ester monomer unit in the acrylic block copolymer: 20% by weight, Kuraray Co., Ltd., Kuraity LA2140)

[0106] (Component D) D-1: Triethyl phosphonoacetate (JC-224 (trade name) manufactured by Johoku Chemical Industry Co., Ltd.) D-2: Stearyl acid phosphate zinc salt (JP-518Zn (trade name) manufactured by Johoku Chemical Industry Co., Ltd.) D-3 (Comparative example): Phosphorus-based stabilizer (tris(2,4-di-tert-butylphenyl) phosphite (ADEKA STAB 2112 (trade name) manufactured by ADEKA Corporation)) D-4 (Comparative example): Phosphorus-based stabilizer (2,4,8,10-tetra-t-butyl-6-[3-(3-methyl-4-hydroxy-5-t-butylphenyl)propoxy]dibenzo[d,f][1,3,2]dioxaphosphepine (Sumitomo Chemical Co., Ltd., Sumilizer GP (trade name))

[0107] (Component E) E-1: UV absorber (Tinuvin 234 (trade name) manufactured by BASF)

[0108] (Other Components) F-1: Hindered phenol-based antioxidant (ADEKA STAB AO-50 (trade name) manufactured by ADEKA CORPORATION) H-1: Mold release agent (fatty acid ester, UNISTAR H-476-S (trade name) manufactured by NOF CORPORATION) I-1: Carbon black masterbatch (base resin: acrylonitrile-styrene resin, carbon black ratio: 40% by weight, ABF-T-8961-MG (trade name) manufactured by Resino Color Kogyo Co., Ltd.)

[0109] (2) Production of Resin Composition The components listed in Tables 1 and 2 were mixed in the proportions listed, and the mixture was fed from the first feed port of an extruder. This mixture was obtained by mixing in a V-blender. For extrusion, a vented twin-screw extruder with a diameter of 30 mm (TEX30A-38.5BW-3V, manufactured by The Japan Steel Works, Ltd.) was used, and the mixture was melt-kneaded at a screw rotation speed of 230 rpm, a discharge rate of 25 kg / h, and a vent vacuum of 3 kPa to obtain pellets. The extrusion temperature from the first feed port to the die was 260°C.

[0110] (3) Evaluation Items The following items were evaluated. The results are shown in Tables 1 and 2. (3-1) Flowability The obtained pellets were dried in a hot air circulation dryer at 110°C for 6 hours, and then the melt volume rate (MVR) was measured using a semi-automatic melt indexer [Semi-automatic melt indexer 2A, manufactured by Toyo Seiki Seisaku-sho, Ltd.] at a temperature of 250°C and a load of 5000 g.

[0111] (3-2) Moist Heat Resistance The obtained pellets were subjected to moist heat treatment for 48 hours under conditions of 120°C and 100% RH using a pressure cooker tester TPC-412 (manufactured by ESPEC Corporation). After the moist heat treatment, the pellets were dried in a hot air circulation dryer at 110°C for 6 hours, and then the MVR was measured in the same manner as in "(3-1) Fluidity", and the MVR increase rate was calculated using the following formula. A smaller MVR increase rate indicates better moist heat resistance. MVR increase rate (%) = [MVR of pellets after moist heat treatment / MVR of pellets before moist heat treatment] x 100

[0112] (3-3) Impact Resistance The obtained pellets were dried in a hot air circulation dryer at 110 ° C for 6 hours, and then molded into plate-shaped test pieces measuring 45 mm long x 50 mm wide x 2 mm thick using an injection molding machine [Toshiba Machine Co., Ltd. EC130XII-4Y] under conditions of a cylinder temperature of 260 ° C and a mold temperature of 70 ° C. Using the obtained plate-shaped test pieces, in accordance with JIS K7211-2, a high-speed puncture impact tester "Hydroshot HTM-1" (Shimadzu Corporation) was used to perform a punching test five times at a punching test speed of 7 mm / sec in an environment of -30 ° C, and the number of ductile fractures at that time was recorded. The value was recorded in the table as the number of ductile fractures before wet heat treatment. In addition, similar test pieces were subjected to wet heat treatment for 1000 hours in a constant temperature and humidity chamber at 90 ° C and 95% RH, and then a punching test was similarly performed to evaluate the number of ductile fractures. The results are shown in the table as "after wet heat".

[0113]

[0114]

Claims

1. A polycarbonate resin composition comprising 100 parts by weight of a resin component consisting of (A) 40 to 90 parts by weight of a polycarbonate resin (component A) and (B) 10 to 60 parts by weight of a copolymer obtained by polymerizing an aromatic vinyl monomer and a vinyl cyanide monomer (component B), (C) 0.5 to 6 parts by weight of an acrylic block copolymer (component C) containing a polymer block containing an acrylic acid ester monomer unit and a polymer block containing a methacrylic acid ester monomer unit, and (D) 0.001 to 1 part by weight of at least one compound (component D) selected from the group consisting of phosphonic acid esters and phosphate metal salts, wherein the content of polymer blocks containing methacrylic acid ester monomer units in component C is 25% by weight or more of all blocks.

2. The resin composition according to claim 1, wherein component B is a copolymer produced by a bulk polymerization method without using a dispersant or an emulsifier.

3. A resin composition according to claim 1 or 2, wherein component D is at least one compound selected from the group consisting of triethylphosphonoacetate and zinc salt of stearyl acid phosphate.

4. The resin composition according to claim 1 or 2, which contains 0.01 to 2.0 parts by weight of (E) a benzotriazole-based ultraviolet absorber (component E) per 100 parts by weight of the resin component.

5. A molded article made of the resin composition according to claim 1 or 2.

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