Thermoplastic resin composition and molded article made therefrom

Abstract

To provide a thermoplastic resin composition which scarcely causes discoloration and strength degradation even in a severe working condition, and is excellent in recyclability, and a molded article composed of the same.SOLUTION: A thermoplastic resin composition contains, with respect to 100 pts.wt. of (A) a thermoplastic resin (component A), 0.001-1 pts.wt. of (B) phosphonic acid ester (component B) having an acid value of 0.01-0.30 mgKOH / g.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to a thermoplastic resin composition and molded articles made therefrom that exhibit minimal discoloration and strength reduction during molding. More specifically, it relates to a thermoplastic resin composition and molded articles made therefrom that exhibit minimal discoloration and strength reduction, even under harsh processing conditions, and also have excellent recyclability. [Background technology]

[0002] Thermoplastic resin compositions are used in a wide range of fields, including housings and components for electrical, electronic, and office automation equipment, interior and exterior parts for automobiles, furniture, musical instruments, and general merchandise. In recent years, in particular, there has been a growing demand for high recyclability in thermoplastic resin compositions to realize a sustainable society. On the other hand, the use of phosphorus compounds as heat stabilizers in thermoplastic resin compositions is widely known. Patent Document 1 discloses the use of specific phosphorus compounds in resins made of polycarbonate resins and polyester resins. Patent Document 2 discloses the use of phosphorus compounds in combination. However, existing methods still lack sufficient heat stability during molding, and in particular, in applications where thin-walled and lightweight designs are required, molding conditions tend to be high, leading to an increasing number of cases where heat stability is insufficient. Furthermore, there is a growing demand for products to be recycled and reused, and there is a growing need to propose materials that can satisfy the requirements for thermoplastic resin compositions that do not discolor or lose strength even under harsh processing conditions and have excellent recyclability. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Patent No. 4983427 [Patent Document 2] Patent No. 5640734 [Overview of the project] [Problems that the invention aims to solve]

[0004] An object of the present invention is to provide a thermoplastic resin composition that exhibits little discoloration and strength reduction even under severe processing conditions and has excellent recyclability, and a molded article made therefrom.

Means for Solving the Problems

[0005] As a result of intensive studies to achieve the above object, the present inventors have found that by blending a phosphonic acid ester having a specific acid value into a thermoplastic resin composition, it is possible to provide a thermoplastic resin composition that exhibits little discoloration and strength reduction even under severe processing conditions and has excellent recyclability, and a molded article made therefrom, thereby arriving at the present invention.

[0006] That is, the present invention is as follows. 1. A thermoplastic resin composition containing 0.001 to 1 part by weight of a phosphonic acid ester (Component B) having an acid value of 0.01 to 0.30 mgKOH / g with respect to 100 parts by weight of a thermoplastic resin (Component A). 2. The thermoplastic resin composition according to item 1 above, wherein Component A is at least one thermoplastic resin selected from the group consisting of (A-1) polycarbonate resin (Component A-1), (A-2) ABS resin (Component A-2), (A-3) polyester resin (Component A-3), (A-4) AS resin (Component A-4), (A-5) PS resin (Component A-5), and (A-6) ASA resin (Component A-6). 3. The thermoplastic resin composition according to item 1 or 2 above, wherein Component A is at least one thermoplastic resin selected from the group consisting of (A-1) polycarbonate resin (Component A-1), (A-2) ABS resin (Component A-2), and (A-3) polyester resin (Component A-3), and the content of Component A-1 is 40 to 100 parts by weight in 100 parts by weight of Component A. 4. The thermoplastic resin composition according to any one of items 1 to 3 above, wherein Component B is triethyl phosphonoacetate. 5. A molded article made of the thermoplastic resin composition according to any one of items 1 to 4 above.

[0007] Hereinafter, the details of the present invention will be described. <Component A: Thermoplastic Resin> The thermoplastic resin used as Component A of the present invention is a polycarbonate resin, an ABS resin, a polyester resin, an AS resin, a PS resin, an AAS resin, an AES resin, a polyamide resin, a polyolefin resin, a fluororesin, a PPS resin, a PEEK resin, a polyarylate resin, a polyacetal resin, etc., and it is preferably at least one thermoplastic resin selected from the group consisting of a polycarbonate resin, an ABS resin, a polyester resin, an AS resin, a PS resin, and an AAS resin. Further, Component A is at least one thermoplastic resin selected from the group consisting of a polycarbonate resin, an ABS resin, and a polyester resin, and it is more preferable that the content of the polycarbonate resin is 40 to 100 parts by weight in 100 parts by weight of Component A. In addition, it is more preferable that the content of the polycarbonate resin is 60 to 100 parts by weight in 100 parts by weight of Component A.

[0008] <A-1 component: polycarbonate resin> The polycarbonate resin used as Component A-1 of the present invention is obtained by reacting a dihydric phenol with a carbonate precursor. Examples of the reaction method include an interfacial polymerization method, a melt transesterification method, a solid-phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.

[0009] Typical examples of divalent phenols used here 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, and 4,4'-(p-phenyl Examples include bis(4-hydroxyphenyl)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 divalent phenols are bis(4-hydroxyphenyl)alkanes, among which bisphenol A is particularly preferred and widely used in terms of impact resistance.

[0010] In the present invention, in addition to bisphenol A-based polycarbonate resins which are general-purpose polycarbonate resins, it is possible to use, as component A-1, special polycarbonate resins produced using other dihydric phenols. For example, as part or all of the dihydric phenol component, 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") are suitable for applications where requirements for dimensional changes due to water absorption and morphological stability are particularly strict. It is preferable to use these dihydric phenols other than BPA in an amount of 5 mol% or more, particularly 10 mol% or more, based on the total amount of the dihydric phenol components constituting the polycarbonate resin. Particularly when high rigidity and better hydrolysis resistance are required, it is particularly preferable that component A constituting the resin composition is one of the copolymerized polycarbonate resins of the following (1) to (3).

[0011] (1) A copolymerized polycarbonate resin in which, in 100 mol% of the dihydric phenol component constituting the polycarbonate resin, BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, still more preferably 45 to 65 mol%), and BCF is 20 to 80 mol% (more preferably 25 to 60 mol%, still more preferably 35 to 55 mol%). (2) A copolymerized polycarbonate resin in which, in 100 mol% of the dihydric phenol component constituting the polycarbonate resin, BPA is 10 to 95 mol% (more preferably 50 to 90 mol%, still more preferably 60 to 85 mol%), and BCF is 5 to 90 mol% (more preferably 10 to 50 mol%, still more preferably 15 to 40 mol%). (3) A copolymer polycarbonate resin in which, of 100 mol% of the divalent 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 Bis-TMC is 20 to 80 mol% (more preferably 25 to 60 mol%, even more preferably 35 to 55 mol%).

[0012] These special polycarbonate resins may be used individually or mixed in appropriate combinations of two or more types. They can also be mixed with commonly used bisphenol A type polycarbonate resins. The manufacturing methods and properties of these special polycarbonate resins are described in detail in, for example, Japanese Patent Publication No. 6-172508, Japanese Patent Publication No. 8-27370, Japanese Patent Publication No. 2001-55435, and Japanese Patent Publication No. 2002-117580.

[0013] Furthermore, among the various polycarbonate resins mentioned above, those whose copolymerization composition and other properties have been adjusted to bring the water absorption rate and Tg (glass transition temperature) within the following ranges exhibit excellent hydrolysis resistance of the polymer itself, as well as significantly superior low warping after molding. Therefore, they are particularly suitable for fields requiring morphological stability. (i) A 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) A 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%.

[0014] Here, the water absorption rate of the polycarbonate resin was measured using a disc-shaped test piece with a diameter of 45 mm and a thickness of 3.0 mm, after immersion in water at 23°C for 24 hours in accordance with ISO 62-1980. The glass transition temperature (Tg) was determined by differential scanning calorimeter (DSC) measurement in accordance with JIS K7121.

[0015] Carbonyl halides, diester carbonates, or haloformates are used as carbonate precursors, specifically including phosgene, diphenyl carbonate, or dihaloformates of divalent phenols.

[0016] When producing a polycarbonate resin by interfacial polymerization of the divalent phenol and the carbonate precursor, a catalyst, an end-terminating agent, an antioxidant to prevent oxidation of the divalent phenol, etc., may be used as needed. The polycarbonate resin of the present invention also includes a branched polycarbonate resin copolymerized with a trifunctional or polyfunctional aromatic compound, a polyester carbonate resin copolymerized with an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid, a copolymerized polycarbonate resin copolymerized with a bifunctional alcohol (including alicyclic), and a polyester carbonate resin copolymerized with both such bifunctional carboxylic acid and bifunctional alcohol. Furthermore, a mixture of two or more of the obtained polycarbonate resins may also be used.

[0017] Branched polycarbonate resins can impart properties such as drip prevention to the thermoplastic resin composition of the present invention. Examples of trifunctional or polyfunctional aromatic compounds used in such branched polycarbonate resins include phloroglucin, phloroglucides, or 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 include trisphenols such as hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acid chlorides, among which 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.

[0018] In branched polycarbonate resins, the structural units derived from polyfunctional aromatic compounds 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%, of the total 100 mol% of structural units derived from divalent phenols and those derived from such polyfunctional aromatic compounds. Furthermore, especially in the case of melt transesterification, branched structural units may be generated as a side reaction, but the amount of such branched structural units is also preferably 0.001 to 1 mol%, more preferably 0.005 to 0.9 mol%, and even more preferably 0.01 to 0.8 mol%, of the total 100 mol% of structural units derived from divalent phenols. 1 It can be calculated by 1H-NMR measurement.

[0019] Among aliphatic difunctional carboxylic acids, α,ω-dicarboxylic acids are preferred. Examples of aliphatic difunctional carboxylic acids include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanediic acid), dodecanediic acid, tetradecanediic acid, octadecanediic acid, and eicosanedioic acid, as well as alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. As for difunctional alcohols, alicyclic diols are more preferred, with examples including cyclohexanedimethanol, cyclohexanediol, and tricyclodecanedimethanol.

[0020] The reaction methods used in the present invention for producing polycarbonate resin, such as interfacial polymerization, molten transesterification, solid-phase transesterification of carbonate prepolymers, and ring-opening polymerization of cyclic carbonate compounds, are well-known methods described in various literatures and patent publications.

[0021] In producing the thermoplastic resin composition of the present invention, the viscosity-average molecular weight of the polycarbonate resin is preferably 12,500 to 32,000, more preferably 16,000 to 28,000, and even more preferably 18,000 to 26,000. Polycarbonate resins with a viscosity-average molecular weight of less than 12,500 may not yield good mechanical properties. On the other hand, resin compositions obtained from polycarbonate resins with a viscosity-average molecular weight exceeding 32,000 may have poor moldability.

[0022] In this invention, the viscosity-average molecular weight is first calculated using the following formula: the specific viscosity (η SP The viscosity of the solution was determined using an Ostwald viscometer from a solution prepared by dissolving 0.7 g of polycarbonate in 100 ml of methylene chloride at 20°C. Specific viscosity (η SP ) = (t-t0) / t0 [t0 is the number of seconds for the methylene chloride to fall, and t is the number of seconds for the sample solution to fall.] The specific viscosity (η) SP The viscosity-average molecular weight M is calculated from the following formula.

[0023] η SP / c = [η] + 0.45×[η] 2 c (where [η] is the intrinsic viscosity) [η] = 1.23×10 -4 M 0.83 c = 0.7 Furthermore, the viscosity average molecular weight of the polycarbonate resin in the thermoplastic resin composition of the present invention is calculated as follows. That is, the composition is mixed with 20 to 30 times its weight of methylene chloride to dissolve the soluble components in the composition. Such soluble components are collected by celite filtration. Then, the solvent in the obtained solution is removed. The solid after solvent removal is dried sufficiently to obtain a solid of the component dissolved in methylene chloride. From a solution obtained by dissolving 0.7 g of such solid in 100 ml of methylene chloride, the specific viscosity at 20°C is determined in the same manner as above, and the viscosity average molecular weight M is calculated from the specific viscosity in the same manner as above.

[0024] As the polycarbonate resin of the present invention, a polycarbonate-polydiorganosiloxane copolymer resin can also be used. The polycarbonate-polydiorganosiloxane copolymer resin is preferably a copolymer resin prepared by copolymerizing a divalent phenol represented by the following general formula (1) and a hydroxyaryl-terminated polydiorganosiloxane represented by the following general formula (3).

[0025]

Chemical formula

[0026] [ka] [In the above general formula (2), R 11 ,R 12 ,R 13 ,R 14 ,R 15 ,R 16 ,R 17 and R 18 Each of these 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 of these 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 carboxyl group. If there are multiple 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.

[0027] [ka] [In the above general formula (3), R 3 , R 4 , R 5 , R 6 , R 7 and R 8 Each of these is independently a hydrogen atom, a C1-C12 alkyl group, or a C6-C12 substituted or unsubstituted aryl group, R 9 and R 10 Each of the following is independently a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, and an alkoxy group with 1 to 10 carbon atoms, where p is a natural number, q is 0 or a natural number, and p+q is a natural number between 10 and 300. X is a divalent aliphatic group with 2 to 8 carbon atoms.

[0028] Examples of divalent phenols (I) represented by 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-H 1,1-bis(4-hydroxyphenyl)fluorene, 2,2-diphenylmethane, 3,1-bis(4-hydroxyphenyl)cyclohexane, 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.

[0029] 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, with 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 being particularly preferred. Among these, 2,2-bis(4-hydroxyphenyl)propane, which has excellent strength and good durability, is the most suitable. These may be used individually or in combination of two or more.

[0030] As the hydroxyaryl-terminated polydiorganosiloxane represented by the above general formula (3), the following compounds are preferably used, for example.

[0031] [ka]

[0032] Hydroxyaryl-terminated polydiorganosiloxanes (II) can be easily produced by hydrosiliculation reaction of olefinic unsaturated carbon-carbon bonded phenols, preferably vinylphenol, 2-allylphenol, isopropenylphenol, and 2-methoxy-4-allylphenol, to the ends of a polysiloxane chain having a predetermined degree of polymerization. Among these, (2-allylphenol)-terminated polydiorganosiloxanes and (2-methoxy-4-allylphenol)-terminated polydiorganosiloxanes are preferred, and (2-allylphenol)-terminated polydimethylsiloxanes and (2-methoxy-4-allylphenol)-terminated polydimethylsiloxanes are particularly preferred. Hydroxyaryl-terminated polydiorganosiloxanes (II) preferably have a molecular weight distribution (Mw / Mn) of 3 or less. Furthermore, in order to exhibit excellent low outgassing and low-temperature impact resistance during high-temperature molding, such a 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 suitable range is exceeded, the amount of outgassing during high-temperature molding increases, and the low-temperature impact resistance may be poor.

[0033] Furthermore, to achieve high impact resistance, the degree of diorganosiloxane polymerization (p+q) of the hydroxyaryl-terminated polydiorganosiloxane(II) is appropriately set to 10-300. This degree of diorganosiloxane polymerization (p+q) is preferably 10-200, more preferably 12-150, and even more preferably 14-100. Below the lower limit of this preferred range, the impact resistance characteristic of polycarbonate-polydiorganosiloxane copolymers is not effectively exhibited, and above the upper limit of this preferred range, appearance defects appear.

[0034] The polydiorganosiloxane content in the polycarbonate-polydiorganosiloxane copolymer resin used in component A-1 is preferably 0.1 to 50% by weight. More preferably, the polydiorganosiloxane content is 0.5 to 30% by weight, and even more preferably 1 to 20% by weight. Above the lower limit of this preferred range, excellent impact resistance and flame retardancy are obtained, and below the upper limit of this preferred range, a stable appearance less affected by molding conditions is easily obtained. The degree of polydiorganosiloxane polymerization and polydiorganosiloxane content are: 1 It can be calculated by 1H-NMR measurement.

[0035] In the present invention, only one hydroxyaryl-terminated polydiorganosiloxane(II) may be used, or two or more may be used.

[0036] Furthermore, to the extent that it does not interfere with the present invention, other comonomers other than the above-mentioned divalent phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II) may be used in combination in a range of 10% by weight or less relative to the total weight of the copolymer.

[0037] In the present invention, a mixed solution containing an oligomer having terminal chloroformate groups is prepared in advance by the reaction of divalent phenol(I) with a carbonate ester-forming compound in a mixture of a water-insoluble organic solvent and an alkaline aqueous solution.

[0038] In producing the divalent phenol(I) oligomer, the entire amount of divalent phenol(I) used in the method of the present invention may be converted into an oligomer at once, or a portion of it may be added as a reaction material to the subsequent interfacial polycondensation reaction as a post-added monomer. The post-added monomer is added to expedite the subsequent polycondensation reaction, and it is not necessary to add it if it is not needed. The method of this oligomer formation reaction is not particularly limited, but it is generally preferable to carry it out in a solvent in the presence of an acid binder.

[0039] The proportion of ester-forming compounds used can be adjusted as appropriate, taking into account the stoichiometric ratio (equivalent) of the reaction. Furthermore, when using gaseous ester-forming compounds such as phosgene, a suitable method is to bubble them into the reaction system.

[0040] 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, or mixtures thereof. The proportion of acid binder used should be determined appropriately, taking into account the stoichiometric ratio (equivalents) of the reaction, as described above. Specifically, it is preferable to use 2 equivalents or a slightly excess amount of acid binder relative to the number of moles of divalent phenol(I) used to form the oligomer (usually 1 mole corresponds to 2 equivalents).

[0041] As the aforementioned solvent, various reaction-inert solvents, such as those used in the production of known polycarbonates, can be used individually or as a mixed solvent. 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.

[0042] There are no particular restrictions on the reaction pressure for oligomer formation; it can be atmospheric pressure, pressurized pressure, 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 polymerization is often exothermic, water cooling or ice cooling is desirable. The reaction time depends on other conditions and cannot be specified in general, but it is usually carried out in 0.2 to 10 hours. The pH range for the oligomer formation reaction is the same as for known interfacial reaction conditions, and the pH is always adjusted to 10 or higher.

[0043] In this invention, a mixed solution containing an oligomer of divalent phenol (I) having terminal chloroformate groups is obtained, and while stirring the mixed solution, a 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, is added to the divalent phenol (I), and the hydroxyaryl-terminated polydiorganosiloxane (II) and the oligomer are subjected to interfacial polycondensation to obtain a polycarbonate-polydiorganosiloxane copolymer.

[0044] [ka] (In the above general formula (3), R 3 , R 4 , R 5 , R 6 , R 7 and R 8 Each of these is independently a hydrogen atom, a C1-C12 alkyl group, or a C6-C12 substituted or unsubstituted aryl group, R 9 and R 10 Each of the following is independently a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, and an alkoxy group with 1 to 10 carbon atoms, where p is a natural number, q is 0 or a natural number, and p+q is a natural number between 10 and 300. X is a divalent aliphatic group with 2 to 8 carbon atoms.

[0045] When carrying out an interfacial polycondensation reaction, an acid binder may be added as appropriate, taking into consideration 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, or mixtures thereof. Specifically, when adding a portion of the hydroxyaryl-terminated polydiorganosiloxane(II) or divalent phenol(I) as described above as a post-added monomer to this reaction step, it is preferable to use 2 equivalents or an excess amount of alkali relative to the total number of moles of the post-added divalent phenol(I) and hydroxyaryl-terminated polydiorganosiloxane(II) (usually 1 mole corresponds to 2 equivalents).

[0046] The polycondensation reaction between the divalent phenol (I) oligomer and the hydroxyaryl-terminated polydiorganosiloxane (II) is carried out by vigorously stirring the above mixture. In such polymerization reactions, end-terminating agents or molecular weight modifiers are commonly used. Examples of end-terminating agents include compounds having a monovalent phenolic hydroxyl group, such as ordinary phenols, p-tert-butylphenol, p-cumylphenol, and tribromophenol, as well as long-chain alkylphenols, aliphatic carboxylic acid chlorides, aliphatic carboxylic acids, alkyl hydroxybenzoates, hydroxyphenylalkylates, and alkyl etherphenols. The amount used is in the range of 100 to 0.5 moles, preferably 50 to 2 moles, per 100 moles of all divalent phenolic compounds used, and it is naturally possible to use two or more compounds in combination.

[0047] To accelerate the polycondensation reaction, a catalyst such as a tertiary amine like triethylamine or a quaternary ammonium salt may be added. The reaction time for such polymerization is preferably 30 minutes or more, and more preferably 50 minutes or more. Optionally, a small amount of antioxidant such as sodium sulfite or hydrosulfide may be added.

[0048] Branching agents can be used in combination with the above-mentioned divalent phenolic compounds to form branched polycarbonate-polydiorganosiloxanes. Examples of trifunctional or polyfunctional aromatic compounds used in such branched polycarbonate-polydiorganosiloxane copolymer resins include phloroglucin, phloroglucid, or 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, and 4-{4-[1 Examples include trisphenols such as 1-bis(4-hydroxyphenyl)ethyl]benzene-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acid chlorides, among which 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 polyfunctional compounds 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%, of the total amount of the polycarbonate-polydiorganosiloxane copolymer resin. 1 It can be calculated by 1H-NMR measurement.

[0049] The reaction pressure can be reduced, atmospheric, or pressurized, but it is usually preferable to use atmospheric pressure or the self-pressure of the reaction system. The reaction temperature is selected from the range of -20 to 50°C, and since polymerization often generates heat, water cooling or ice cooling is desirable. The reaction time varies depending on other conditions such as the reaction temperature and cannot be specified in general terms, but it is usually carried out in 0.5 to 10 hours.

[0050] Depending on the circumstances, the obtained polycarbonate-polydiorganosiloxane copolymer resin may be subjected to appropriate physical treatment (mixing, fractionation, etc.) and / or chemical treatment (polymer reaction, crosslinking, partial decomposition, etc.) to obtain the desired reduced viscosity [η SP It can also be obtained as a polycarbonate-polydiorganosiloxane copolymer resin of [c].

[0051] The resulting reaction product (crude product) can be recovered as a polycarbonate-polydiorganosiloxane copolymer resin of the desired purity (degree of purification) by various post-treatment methods, such as known separation and purification methods.

[0052] The average size of polydiorganosiloxane domains in polycarbonate-polydiorganosiloxane copolymer resin molded articles is preferably in the range of 1 to 40 nm. More preferably, this average size is 1 to 30 nm, and even more preferably 5 to 25 nm. Below the lower limit of this preferred range, impact resistance and flame retardancy may not be sufficiently exhibited, and above the upper limit of this preferred range, impact resistance may not be stably exhibited.

[0053] The average domain size and normalized dispersion of polydiorganosiloxane domains in the polycarbonate-polydiorganosiloxane copolymer resin molded product of this invention were evaluated by small-angle X-ray scattering (SAXS). Small-angle X-ray scattering is a method for measuring diffuse scattering and diffraction occurring in the small-angle region with a scattering angle (2θ) < 10° or less. In this small-angle X-ray scattering method, if there are regions with different electron densities of about 1 to 100 nm in size in the material, diffuse scattering of X-rays is measured due to the difference in electron density. The particle size of the object to be measured is determined based on this scattering angle and scattering intensity. In the case of polycarbonate-polydiorganosiloxane copolymer resin, which has an aggregated structure in which polydiorganosiloxane domains are dispersed in a polycarbonate polymer matrix, diffuse scattering of X-rays occurs due to the difference in electron density between the polycarbonate matrix and the polydiorganosiloxane domains. The scattering intensity I is measured at each scattering angle (2θ) in the range of less than 10° to obtain a small-angle X-ray scattering profile. Assuming that the polydiorganosiloxane domains are spherical and that there is variability in the particle size distribution, the average size and particle size distribution (normalized variance) of the polydiorganosiloxane domains are determined by simulating with commercially available analysis software using a hypothetical particle size and a hypothetical particle size distribution model. Small-angle X-ray scattering allows for accurate, simple, and reproducible measurement of the average size and particle size distribution of polydiorganosiloxane domains dispersed in a polycarbonate polymer matrix, which cannot be accurately measured by transmission electron microscopy. The average domain size refers to the numerical average of the individual domain sizes. Normalized variance refers to a parameter that normalizes the spread of the particle size distribution by the average size. Specifically, it is the value obtained by normalizing the variance of the polydiorganosiloxane domain size by the average domain size, and is expressed by the following equation (1).

[0054]

number

[0055] The terms "average domain size" and "normalized dispersion" used in connection with the present invention refer to measured values obtained by measuring a 1.0 mm thick portion of a three-stage plate produced by the method described in the Examples by such a small-angle X-ray scattering method. Further, analysis was performed using an isolated particle model that does not consider particle-particle interaction (particle-particle interference).

[0056] <A-2 component: ABS resin> The ABS resin used as component A-2 of the present invention is a copolymer obtained by graft polymerization of acrylonitrile and styrene onto polybutadiene. Styrene and α-methylstyrene are particularly preferred as the styrene. The proportion of the component grafted onto the polybutadiene is preferably 95 to 20% by weight, and particularly preferably 90 to 50% by weight, of 100% by weight of the ABS resin component. Furthermore, it is preferable that the acrylonitrile is 5 to 50% by weight and the styrene is 95 to 50% by weight, based on the total amount of acrylonitrile and styrene of 100% by weight. In addition, methyl (meth)acrylate, ethyl acrylate, maleic anhydride, N-substituted maleimide, etc., can be mixed and used as part of the component graft polymerized onto the polybutadiene, and it is preferable that the content of these is 15% by weight or less of the ABS resin component. Furthermore, various conventionally known initiators, chain transfer agents, emulsifiers, etc., can be used in the reaction as needed. In the ABS resin of the present invention, the particle size of polybutadiene is preferably 0.1 to 5.0 μm, more preferably 0.2 to 3.0 μm, and particularly preferably 0.3 to 1.5 μm. The particle size distribution of such polybutadiene can be either a single distribution or one with two or more peaks, and furthermore, in terms of morphology, the particles may form a single phase, or they may have a salami structure due to the inclusion of an occluded phase around the particles. It is also well known that ABS resins contain copolymers of acrylonitrile and styrene that are not grafted onto the diene rubber component, and the ABS resin of the present invention may also contain free polymer components generated during such polymerization. The reduced viscosity of such free acrylonitrile and styrene copolymer is preferably 0.2 to 1.0 dl / g, and more preferably 0.3 to 0.7 dl / g at 30°C. Furthermore, the proportion of grafted acrylonitrile and styrene is preferably 20-200% (by weight) relative to polybutadiene, and more preferably 20-70%. Such ABS resin may be produced by any of the following methods: bulk polymerization, suspension polymerization, or emulsion polymerization, but bulk polymerization is particularly preferred.In the case of bulk polymerization, since it substantially does not contain alkali metal salts and the like derived from emulsifiers and the like, it becomes possible to better maintain the thermal stability of the resin composition. Also, the copolymerization method may be carried out in one stage or in multiple stages. Further, a blend obtained by separately copolymerizing acrylonitrile and styrene with the ABS resin obtained by such a production method can also be preferably used.

[0057] <A-3 component: Polyester resin> The polyester resin used as the A-3 component of the present invention is preferably a polyester resin in which 70 mol% or more, more preferably 90 mol% or more, and most preferably 99 mol% or more of 100 mol% of the dicarboxylic acid component forming the polyester is an aromatic dicarboxylic acid.

[0058] Examples of this dicarboxylic acid include terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2,5-dichloroterephthalic acid, 2-methylterephthalic acid, 4,4-stilbenedicarboxylic acid, 4,4-biphenyldicarboxylic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, bisbenzoic acid, bis(p-carboxyphenyl)methane, anthracenedicarboxylic acid, 4,4-diphenyletherdicarboxylic acid, 4,4-diphenoxyethanedicarboxylic acid, 5-Na sulfoisophthalic acid, ethylene-bis-p-benzoic acid, and the like. These dicarboxylic acids can be used alone or in combination of two or more. In the polyester resin of the present invention, in addition to the above aromatic dicarboxylic acids, an aliphatic dicarboxylic acid component of less than 30 mol% can be copolymerized. Specific examples thereof include adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and the like.

[0059] Examples of the diol component of the present invention include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, trans- or cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, decamethylene glycol, cyclohexanediol, p-xylenediol, bisphenol A, tetrabromobisphenol A, and tetrabromobisphenol A-bis(2-hydroxyethyl ether). These can be used individually or in combination of two or more. Preferably, the divalent phenol content in the diol component is 30 mol% or less.

[0060] Specific examples of polyester resins include polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate (PBT), polyhexylene terephthalate, polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyethylene-1,2-bis(phenoxy)ethane-4,4'-dicarboxylate, and copolymerized polyester resins such as polyethylene isophthalate / terephthalate copolymers and polybutylene terephthalate / isophthalate copolymers.

[0061] Furthermore, the end group structure of the polyester resin used in the present invention is not particularly limited, and in addition to cases where the proportion of hydroxyl groups and carboxyl groups in the end groups is approximately equal, the proportion of one may be greater than the other. Moreover, the end groups may be encapsulated by reacting them with a compound that is reactive with them.

[0062] The polyester resin used in the present invention is produced by polymerizing a dicarboxylic acid component and a diol component while heating in the presence of a polycondensation catalyst containing titanium, germanium, antimony, etc., according to conventional methods, and discharging the by-product water or lower alcohol from the system. For example, germanium-based polymerization catalysts include germanium oxides, hydroxides, halides, alcoholates, phenolates, etc. More specifically, germanium oxide, germanium hydroxide, germanium tetrachloride, tetramethoxygermanium, etc. In addition, the present invention can also use compounds such as manganese, zinc, calcium, and magnesium, which are used in the transesterification reaction that is a known precursor to polycondensation, and it is also possible to deactivate such catalysts with a phosphoric acid or phosphorous acid compound, etc., after the transesterification reaction is completed and then perform polycondensation. Furthermore, the polyester resin can be produced using either a batch method or a continuous polymerization method.

[0063] Furthermore, among the polyester resins mentioned above, polyethylene terephthalate is particularly preferred. The polyethylene terephthalate of the present invention is a polymer obtained by polycondensation reaction of terephthalic acid or its derivatives and 1,4-ethanediol or its derivatives, and as described above, it includes copolymers with other dicarboxylic acid components and other alkylene glycol components.

[0064] The end group structure of polyethylene terephthalate is not particularly limited as described above, but it is more preferable that the terminal carboxy group is less than the terminal hydroxyl group. Regarding the production method, the above various methods can be adopted, but a continuous polymerization type is preferred. This is because its quality stability is high and it is also advantageous in terms of cost. Furthermore, it is preferable to use an organic titanium compound as the polymerization catalyst. This is because it tends to have little influence on transesterification reactions and the like. Specific preferable examples of such an organic titanium compound include titanium tetrabutoxide, titanium isopropoxide, titanium oxalate, titanium acetate, titanium benzoate, titanium trimellitate, and the reaction product of tetrabutyl titanate and trimellitic anhydride. The usage amount of the organic titanium compound is preferably in a ratio such that the titanium atom is 3 to 12 mg atom% with respect to the acid component constituting polyethylene terephthalate.

[0065] The molecular weight of the polyester resin of the present invention is not particularly limited, but the intrinsic viscosity measured at 35 °C using o-chlorophenol as a solvent is preferably 0.5 to 1.5, and particularly preferably 0.6 to 1.2.

[0066] <A-4 component: AS resin> The AS resin used as the A-4 component of the present invention is a copolymer of acrylonitrile and styrene. The AS resin may have high stereoregularity such as syndiotactic polystyrene by using a catalyst such as a metallocene catalyst during its production. Furthermore, in some cases, polymers and copolymers with a narrow molecular weight distribution, block copolymers, and polymers and copolymers with high stereoregularity obtained by methods such as anionic living polymerization and radical living polymerization can also be used.

[0067] <A-5 component: PS resin> The PS resin used as the A-5 component of the present invention is a polymer of styrene.

[0068] <A-6 component: AAS resin> The AAS resin used as the A-6 component of the present invention is a copolymer composed of acrylonitrile, styrene, and an acrylic rubber component.

[0069] <Component B: Phosphonic acid ester> As the phosphonic acid ester used in the present invention, phosphonic acid monoester, phosphonic acid diester, and phosphonic acid triester can be used, but phosphonic acid triester is preferred. Various combinations of esters with carbon numbers from 1 to 22 can be used, but triethyl phosphonoacetate is most preferred. The acid value of the phosphonic acid ester is 0.01 - 0.30 mgKOH / g, preferably 0.01 - 0.20 mgKOH / g, more preferably 0.05 - 0.15 mgKOH / g. If the acid value is less than 0.01 mgKOH / g, it is not practical in production, and when it is greater than 0.30 mgKOH / g, discoloration and strength reduction during molding cannot be prevented. The acid value was measured using a potentiometric titration apparatus, and an alcohol solution of the phosphonic acid ester was titrated with a KOH alcohol solution.

[0070] The content of Component B is 0.001 - 1 part by weight, preferably 0.01 - 0.1 part by weight, more preferably 0.01 - 0.07 part by weight, based on 100 parts by weight of Component A. When the content of Component B is less than 0.001 part by weight or exceeds 1 part by weight, discoloration and strength reduction during molding cannot be prevented.

[0071] <Other components> The thermoplastic resin composition of the present invention can be blended with various fillers, flame retardants, and other additives as long as the object of the present invention is not impaired.

[0072] <Manufacture of thermoplastic resin composition> Any method can be used to produce the thermoplastic resin composition of the present invention. For example, one method involves thoroughly mixing component A, component B, and optionally other components using pre-mixing means such as a V-type blender, Henschel mixer, mechanochemical device, or extruder, then granulating the pre-mixture using an extruder or briquetting machine as needed, followed by melt-kneading in a melt-kneader such as a vented twin-screw extruder, and finally pelletizing with a pelletizer.

[0073] Other methods include supplying each component independently to a melting and mixing machine, such as a vented twin-screw extruder, or pre-mixing some of the components and then supplying them separately to the melting and mixing machine along with the remaining components. An example of a method for pre-mixing some of the components is to pre-mix the components other than component A beforehand, and then mix them with the thermoplastic resin of component A or supply them directly to the extruder.

[0074] One method of pre-mixing is, for example, if component A is in powder form, a masterbatch of the additive can be produced by blending a portion of the powder with the additive to be blended, and then using this masterbatch. Another method is to supply one component independently from the middle of the melt extruder. If there is a liquid component to be blended, a so-called liquid injection device or liquid additive device can be used to supply it to the melt extruder.

[0075] Preferably, an extruder equipped with a vent capable of removing moisture from the raw material and volatile gases generated from the molten and kneaded resin is used. A vacuum pump is preferably installed in the vent to efficiently discharge the generated moisture and volatile gases to the outside of the extruder. It is also possible to install a screen in the zone in front of the extruder die to remove foreign matter mixed into the extrusion raw material, thereby removing foreign matter from the resin composition. Examples of such screens include wire mesh, screen changers, and sintered metal plates (disc filters, etc.).

[0076] Other types of melting and mixing machines include twin-screw extruders, Banbury mixers, mixing rolls, single-screw extruders, and multi-screw extruders with three or more shafts.

[0077] As described above, the extruded resin is either directly cut and pelletized, or strands are formed and then cut in a pelletizer to form pellets. If it is necessary to reduce the influence of external dust and other contaminants during pelletization, it is preferable to clean the atmosphere around the extruder. Furthermore, in the production of such pellets, various methods already proposed for polycarbonate resins for optical discs can be used to appropriately narrow the shape distribution of the pellets, reduce miscuts, reduce fine powder generated during transportation or transport, and reduce air bubbles (vacuum bubbles) generated inside the strands and pellets. These formulations can enable high-cycle molding and reduce the rate of defects such as silver. The shape of the pellets can be general shapes such as cylinders, prismatics, and spheres, but cylinders are more preferable. The diameter of such cylinders is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and even more preferably 2 to 3.3 mm. On the other hand, the length of the cylinders is preferably 1 to 30 mm, more preferably 2 to 5 mm, and even more preferably 2.5 to 3.5 mm. [Effects of the Invention]

[0078] The thermoplastic resin composition of the present invention exhibits minimal discoloration and strength reduction even under harsh processing conditions, and also boasts excellent recyclability. Therefore, it is useful in applications requiring thin walls and lightweight construction under high-temperature molding conditions, as well as in cases where products are recycled and reused. The resulting industrial benefits are extremely significant. [Modes for carrying out the invention]

[0079] The present inventors consider the best possible form of the present invention to be a combination of the preferred ranges of the above requirements, and a representative example is described in the following embodiments. Of course, the present invention is not limited to these forms. [Examples]

[0080] The present invention will be further explained with reference to the following examples, but is not limited thereto. The following items were evaluated: (i) Discoloration during stagnation Pellets obtained from each composition of the examples were dried in a hot air dryer at 100°C for 5 hours. Using an injection molding machine [Sumitomo Heavy Industries, Ltd. SG150U·SM IV], 100 shots of 150mm × 150mm × 2mmt square plates were continuously molded at the temperatures shown in the table. The operation of the molding machine was then stopped, and the resin was allowed to remain in the cylinder. After 15 minutes, square plates were molded again, and the hue of the square plates before and after the retention period was measured using a Tokyo Denshoku color analyzer TC-1800MKII, and the color difference (ΔE) before and after the retention period was calculated.

[0081] (ii) Strength retention rate during retention Using the square plates used in "(i) Discoloration during retention," a high-speed surface impact test was conducted, and the fracture energy of the square plates before and after retention was measured. The strength retention rate before and after retention was calculated using the following formula. The measurements were performed using a HydroShot HTM-1 manufactured by Shimadzu Corporation at 23°C and a test speed of 7 m / s. Strength retention rate (%) = [Fracture energy after retention / Fracture energy before retention] × 100

[0082] (iii) Recyclability The square plates used in "(i) Discoloration during retention" were left horizontally outdoors in Midori Ward, Chiba City for one year, then crushed and reshaped into square plates. The hue and fracture energy of the square plates before retention and the reshaped square plates were measured using the same method as in "(i) Discoloration during retention" and "(ii) Strength retention rate during retention," and the color difference (ΔE) and strength retention rate of the two were measured.

[0083] [Examples 1-12, Comparative Examples 1-5] Resin compositions consisting of the proportions shown in Table 1 were prepared as follows. The explanation will follow the symbols in the table below. Each component in the proportions shown in the table was weighed, uniformly mixed using a tumbler, and the mixture was fed into an extruder to prepare the resin composition. A vented twin-screw extruder (TEX-30XSST, manufactured by Japan Steel Works Ltd., fully engaged, co-rotating, double-threaded screw) was used. The extrusion conditions were a discharge rate of 20 kg / h, a screw rotation speed of 150 rpm, and a vent vacuum of 3 kPa. The extrusion temperature was as shown in the table. Using the obtained pellets, test pieces for evaluation were molded using an injection molding machine in the manner described above. The evaluation results are shown in Table 1. The symbols in Table 1 indicate the following components.

[0084] (Component A: Thermoplastic resin) A-1-1: Aromatic polycarbonate resin (polycarbonate resin powder with a viscosity-average molecular weight of 20,700, manufactured by conventional methods from bisphenol A and phosgene; manufactured by Teijin Limited, product name: Panlite L-1225WS) A-1-2: Modified polycarbonate resin powder with a viscosity-average molecular weight of 22,300 obtained by the following manufacturing method. In a reactor equipped with a thermometer, stirrer, and reflux condenser, 4,229 parts of 48% sodium hydroxide aqueous solution and 20,000 parts of deionized water were charged. 2,191 parts of 1,1-bis(4-hydroxy-3-methylphenyl)propane (hereinafter abbreviated as Bis-1), 1,951 parts of bisphenol A, and 8.3 parts of hydrosulfite were dissolved in these mixtures. Then, 11,620 parts of methylene chloride were added, and under stirring, 2,200 parts of phosgene were blown in over approximately 60 minutes at 15-25°C. After the phosgene blowing was complete, 704 parts of 48% sodium hydroxide aqueous solution and 102 parts of p-tert-butylphenol were added, stirring was resumed, and after emulsification, 4.32 parts of triethylamine were added, and the reaction was completed by stirring for 1 hour at 28-33°C. After the reaction was complete, the product was diluted with methylene chloride and washed with water, then acidified with hydrochloric acid and washed with water again. Further washing with water was repeated until the conductivity of the aqueous phase was approximately the same as that of deionized water to obtain a methylene chloride solution of polycarbonate resin. Next, this solution was passed through a filter with a mesh size of 0.3 μm and then dropped into warm water in a kneader with an isolation chamber having a foreign matter outlet in the bearing section. The polycarbonate resin was flakebed while the methylene chloride was removed by distillation, and the liquid-containing flakes were subsequently crushed and dried to obtain a powder. A-1-3: Polycarbonate-polydiorganosiloxane copolymer resin (viscosity-average molecular weight 19,800, PDMS content 4.2%, PDMS degree of polymerization 37) A-2: ABS resin (manufactured by Japan A&L Co., Ltd., Suntac AT-07 (product name), butadiene rubber component approximately 17.5% by weight, weight-average rubber particle size 1.2 μm, manufactured by bulk polymerization) A-3: Polyethylene terephthalate (manufactured by Teijin Limited, TRN-8550FF (product name)) A-4: AS resin (manufactured by Nippon A&L Co., Ltd., product name: Lightac A BS-207) A-5: PS resin (Manufactured by IRPC Public Company Limited, product name GP-110) A-6: AAS resin (777K (product name) manufactured by INEOS)

[0085] (Component B: Phosphonic acid ester) B-1: Triethylphosphonoacetate (manufactured by Johoku Chemical Industry Co., Ltd., JC-224 (product name), acid value 0.08 mg KOH / g) B-2 (Comparative Example): Triethylphosphonoacetate (Solvay, Inc., Acid Value 0.39 mg KOH / g) B-3: Triethylphosphonoacetate (mixture of B-1 and B-2 (weight ratio 1:1), acid value 0.23 mg KOH / g)

[0086] [Table 1]

Claims

1. A thermoplastic resin composition comprising (A) 100 parts by weight of at least one thermoplastic resin (component A) selected from the group consisting of (A-1) polycarbonate resin (component A-1), (A-2) ABS resin (component A-2), (A-4) AS resin (component A-4), (A-5) PS resin (component A-5), and (A-6) AAS resin (component A-6), and (B) 0.001 to 1 part by weight of a phosphonic acid ester (component B) having an acid value of 0.01 to 0.30 mgKOH / g.

2. The thermoplastic resin composition according to claim 1, wherein component A is at least one thermoplastic resin selected from the group consisting of (A-1) polycarbonate resin (component A-1) and (A-2) ABS resin (component A-2), and the content of component A-1 is 40 to 100 parts by weight per 100 parts by weight of component A.

3. The thermoplastic resin composition according to claim 1 or 2, wherein component B is triethylphosphonoacetate.

4. A molded article comprising the thermoplastic resin composition described in claim 1 or 2.

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