Polycarbonate resin composition and molded article obtained by molding the same

Abstract

To provide a polycarbonate resin composition which is excellent in dispersibility and flame retardancy of polytetrafluoroethylene when a reclaimed polycarbonate-based resin is used at a high ratio, and is excellent in recyclability when a molded article of the resin composition is recycled, and a molded article obtained by molding the same.SOLUTION: A polycarbonate resin composition contains, with respect to 100 pts.wt. of 0 to 30 pts.wt. of (A) a polycarbonate-based resin (component A) and 100 to 70 pts.wt. of a reclaimed polycarbonate-based resin (component B), 1 to 25 pts.wt. of (C) a phosphorus-based flame retardant (component C), and 0.05 to 4 pts.wt. of (D) a polytetrafluoroethylene-based mixed body (component D) composed of polytetrafluoroethylene particles and a styrenic organic polymer, which is obtained by suspension polymerization.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polycarbonate resin composition and a molded article obtained by molding the same. More specifically, the present invention relates to a resin composition comprising a polycarbonate resin, a recycled polycarbonate resin, a phosphorus-based flame retardant, and a polytetrafluoroethylene mixture obtained by suspension polymerization and comprising polytetrafluoroethylene particles and a styrene-based organic polymer, the polycarbonate resin composition having excellent polytetrafluoroethylene dispersibility and flame retardancy when a high proportion of recycled polycarbonate resin is used, and a molded article obtained by molding the same. [Background technology]

[0002] Polycarbonate resins are generally used in a wide range of applications, including machine parts, automobile parts, office equipment such as printers and copiers, and electrical and electronic components, due to their excellent properties, including transparency, impact resistance, heat resistance, dimensional stability, and flame retardancy. Office equipment and electrical and electronic components, in particular, require high flame retardancy for safety reasons, in order to prevent fires caused by high temperatures. Furthermore, in recent years, growing awareness of environmental protection has led to a strong social demand for the recycling of resins, and regulations are being tightened. In response to this demand, there is a growing demand for the use of recycled resins in products such as office equipment and electrical and electronic components, and there is an increasing demand for polycarbonate resin compositions containing a high proportion of recycled resin.

[0003] Examples of raw materials for recycled polycarbonate resins (recycled polycarbonate resins) include various glazing materials, such as soundproof walls, automobile windows, translucent roofing materials, and automobile sunroofs; transparent components, such as windshields and automobile headlamp lenses; containers, such as water bottles; light guide plates; eyeglass lenses; and optical recording media. Also usable are non-conforming products, crushed products obtained from sprues and runners, and pellets obtained by melting these. Furthermore, there is a strong demand for further recycling and reuse of products made from the above-mentioned recycled materials, and there is an increasing demand for polycarbonate resin compositions that do not deteriorate in flame retardancy even under harsh processing conditions and have excellent recyclability.

[0004] The use of phosphorus-based flame retardants and polytetrafluoroethylene is a widely known method for imparting flame retardancy to polycarbonate resins, and it has been disclosed that the use of specific polycarbonate resins provides a high level of flame retardancy (Patent Documents 1 and 2). However, when a high proportion of recycled materials is used, polytetrafluoroethylene tends to aggregate during production, which deteriorates flame retardancy, resulting in insufficient flame retardancy. A production process that achieves high flame retardancy and mechanical properties while using recycled materials has also been disclosed (Patent Document 3). However, this does not discuss the aggregation of polytetrafluoroethylene, and furthermore, when products using the resin composition are reused, the flame retardancy under harsh processing conditions is insufficient, resulting in insufficient recyclability. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2023-143264 [Patent Document 2] Japanese Patent Application Publication No. 10-298418 [Patent Document 3] WO2023 / 089929 publication Summary of the Invention [Problem to be solved by the invention]

[0006] In view of the above, an object of the present invention is to provide a polycarbonate resin composition that exhibits excellent dispersibility of polytetrafluoroethylene and excellent flame retardancy when a high proportion of recycled polycarbonate resin is used, and that exhibits excellent recyclability when attempting to reuse molded articles of the resin composition, and a molded article obtained by molding the same. [Means for solving the problem]

[0007] As a result of extensive research conducted by the present inventors to solve the above-mentioned problems, they discovered that the above-mentioned object can be achieved by adding a specific amount of a polytetrafluoroethylene-based mixture consisting of recycled polycarbonate-based resin, a phosphorus-based flame retardant, and polytetrafluoroethylene particles and a styrene-based organic polymer obtained by suspension polymerization to a polycarbonate-based resin, and thus completed the present invention.

[0008] That is, the present invention is as follows. (Configuration 1) A polycarbonate resin composition comprising 100 parts by weight of a total of 0 to 30 parts by weight of (A) a polycarbonate resin (component A) and 100 to 70 parts by weight of (B) a recycled polycarbonate resin (component B), with 1 to 25 parts by weight of (C) a phosphorus-based flame retardant (component C) and 0.05 to 4 parts by weight of (D) a polytetrafluoroethylene mixture (component D) obtained by suspension polymerization and consisting of polytetrafluoroethylene particles and a styrene-based organic polymer. (Configuration 2) 2. The polycarbonate resin composition according to the above item 1, characterized in that it contains 0.01 to 15 parts by weight of an impact modifier (E) (Component E) per 100 parts by weight of the total of Components A and B. (Configuration 3) 3. The polycarbonate resin composition according to the above-mentioned configuration 1 or 2, characterized in that it contains 0.01 to 15 parts by weight of (F) a silicate mineral (component F) per 100 parts by weight of the total of components A and B. (Configuration 4) A molded article obtained by molding the resin composition according to any one of the above configurations 1 to 3.

Advantages of the Invention

[0009] The resin composition of the present invention is excellent in the dispersibility and flame retardancy of polytetrafluoroethylene when a high proportion of recycled polycarbonate-based resin is used, and is excellent in recyclability when attempting to reuse the molded article of the resin composition. Therefore, the effects of the present invention are particularly significant for the realization of a sustainable society.

Modes for Carrying Out the Invention

[0010] Hereinafter, the details of the present invention will be described.

[0011] <Component A: Polycarbonate-based resin> The polycarbonate-based 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 a carbonate prepolymer, and ring-opening polymerization of a cyclic carbonate compound.

[0012] Representative examples of dihydric phenols 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.

[0013] In the present invention, in addition to bisphenol A-based polycarbonate resins, which are general-purpose polycarbonate resins, special polycarbonate resins produced using other dihydric phenols can be used 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 shape 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 hydrolysis 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). (1) 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%, and even more preferably 45 to 65 mol%) and BCF accounts for 20 to 80 mol% (more preferably 25 to 60 mol%, and even more preferably 35 to 55 mol%). (2) A copolymer polycarbonate resin in which, based on 100 mol% of the dihydric phenol components constituting the polycarbonate resin, BPA accounts for 10 to 95 mol% (more preferably 50 to 90 mol%, and even more preferably 60 to 85 mol%) and BCF accounts for 5 to 90 mol% (more preferably 10 to 50 mol%, and even more preferably 15 to 40 mol%). (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%, and even more preferably 45 to 65 mol%) and Bis-TMC accounts for 20 to 80 mol% (more preferably 25 to 60 mol%, and even more preferably 35 to 55 mol%).

[0014] 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-6-172508, JP-A-8-27370, JP-A-2001-55435, and JP-A-2002-117580.

[0015] Among the various polycarbonate resins mentioned above, those in which the copolymer composition and the like are adjusted to bring the water absorption rate and Tg (glass transition temperature) into the ranges described below have good hydrolysis resistance of the polymer itself and are remarkably excellent in terms of low warpage after molding, and are therefore particularly suitable in fields where dimensional stability is required. (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 of 0.10 to 0.30%, preferably 0.13 to 0.30%, more preferably 0.14 to 0.27%.

[0016] Here, the water absorption rate of polycarbonate resin is a value measured by using a disk-shaped test piece with 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 then measuring the moisture content. Also, Tg (glass transition temperature) is a value determined by differential scanning calorimetry (DSC) measurement in accordance with JIS K7121.

[0017] 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.

[0018] When producing a polycarbonate resin by interfacial polymerization of the dihydric phenol and carbonate precursor, 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.

[0019] The branched polycarbonate resin can impart anti-drip properties to the resin composition of the present invention. Examples of trifunctional or higher polyfunctional aromatic compounds used in such branched polycarbonate 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- 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.

[0020] 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% out of the total 100 mol% of the structural units derived from dihydric phenols and the structural units derived from such polyfunctional aromatic compounds. In particular, 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% out of the total 100 mol% of the structural units derived from dihydric phenols. The proportion of such branched structures is 1 It can be calculated by H-NMR measurement.

[0021] The aliphatic bifunctional carboxylic acid is preferably an α,ω-dicarboxylic acid. Preferred examples of the aliphatic bifunctional carboxylic acid include linear 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 bifunctional alcohol is more preferably an alicyclic diol, such as cyclohexanedimethanol, cyclohexanediol, and tricyclodecanedimethanol.

[0022] 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.

[0023] The viscosity average molecular weight (M) of the polycarbonate resin is not particularly limited, but is preferably 1.8×10 4 ~4.0×10 4 and more preferably 2.0 × 10 4 ~3.5×10 4 , and more preferably 2.2 × 10 4 ~3.0×10 4 The viscosity average molecular weight is 1.8 × 10 4 On the other hand, polycarbonate resins with a viscosity average molecular weight of less than 4.0 × 10 may not be able to provide good mechanical properties. 4 Resin compositions obtained from polycarbonate resins exceeding this range may be inferior in versatility due to poor flowability during injection molding.

[0024] The polycarbonate resin may be a mixture of resins having a viscosity average molecular weight outside the above range. 4) the entropy elasticity of the resin is improved. As a result, good molding processability is exhibited 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 resin. In a more preferred embodiment, component A has a viscosity average molecular weight of 7×10 4 ~3×10 5 Polycarbonate resin (A-1-1 component) and viscosity average molecular weight 1 × 10 4 ~3×10 4 The viscosity average molecular weight of the polycarbonate resin (A-1-2 component) is 1.6 × 10 4 ~3.5×10 4 A polycarbonate resin (component A-1) (hereinafter, sometimes referred to as a "polycarbonate resin containing a high molecular weight component") having the formula:

[0025] In such a polycarbonate resin containing a high molecular weight component (component A-1), the molecular weight of component A-1-1 is 7 × 10 4 ~2×10 5 is preferable, and more preferably 8×10 4 ~2×10 5 , and more preferably 1 × 10 5 ~2×10 5 , particularly preferably 1 × 10 5 ~1.6×10 5 The molecular weight of component A-1-2 is 1 × 10 4 ~2.5×10 4 is preferable, and more preferably 1.1 × 10 4 ~2.4×10 4 , and more preferably 1.2 × 10 4 ~2.4×10 4 , particularly preferably 1.2 × 10 4 ~2.3×10 4 is.

[0026] 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 component A-1-1 accounts for 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, of 100% by weight of component A-1.

[0027] Methods for preparing component A-1 include: (1) a method in which component A-1-1 and component A-1-2 are polymerized independently and then mixed; (2) a method in which a polycarbonate resin that shows multiple polymer peaks in a molecular weight distribution chart obtained by GPC, as typified by the method disclosed in Japanese Patent Laid-Open Publication No. 5-306336, is produced in the same system, and the polycarbonate resin is produced so as to satisfy the conditions for component A-1 of the present invention; and (3) a method in which a polycarbonate resin obtained by such a production method (production method (2)) is mixed with component A-1-1 and / or component A-1-2 that have been separately produced.

[0028] The viscosity average molecular weight in the present invention is determined by first calculating the specific viscosity (η 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. Specific viscosity (η SP )=(t-t0) / t0 [t0 is the number of seconds that methylene chloride falls, and t is the number of seconds that the sample solution falls] The calculated specific viscosity (η SP ) and calculate the viscosity average molecular weight M using the following formula: 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 The viscosity average molecular weight of the polycarbonate resin in the polycarbonate 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.

[0029] 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):

[0030] [ka]

[0031] [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):

[0032] [ka]

[0033] [In the above general formula (2), R 11 ,R 12 ,R 13 ,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 multiple groups, they may be the same or different; g is an integer of 1 to 10, and h is an integer of 4 to 7.

[0034] [ka]

[0035] [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 10are 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 of 10 to 300. X is a divalent aliphatic group having 2 to 8 carbon atoms.

[0036] 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. 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, as it has excellent strength and good durability. These may be used alone or in combination.

[0037] As the hydroxyaryl-terminated polydiorganosiloxane represented by the above general formula (3), for example, the compounds shown below are preferably used.

[0038] [ka]

[0039] Hydroxyaryl-terminated polydiorganosiloxanes (II) can be easily produced by hydrosilylation of a phenol having an olefinically unsaturated carbon-carbon bond, preferably vinylphenol, 2-allylphenol, isopropenylphenol, or 2-methoxy-4-allylphenol, at the end 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, with (2-allylphenol)-terminated polydimethylsiloxanes and (2-methoxy-4-allylphenol)-terminated polydimethylsiloxanes being particularly preferred. The molecular weight distribution (Mw / Mn) of the hydroxyaryl-terminated polydiorganosiloxanes (II) is preferably 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.

[0040] Furthermore, in order to achieve high 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.

[0041] The polydiorganosiloxane content of the polycarbonate-polydiorganosiloxane copolymer resin 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 easily achieved. The polydiorganosiloxane polymerization degree and polydiorganosiloxane content are 1 It can be calculated by H-NMR measurement.

[0042] In the present invention, the hydroxyaryl-terminated polydiorganosiloxane (II) may be used alone or in combination of two or more.

[0043] Furthermore, other comonomers than the dihydric phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II) may be used in combination in an amount of up to 10% by weight based on the total weight of the copolymer, provided that this does not interfere with the present invention.

[0044] In the present invention, a mixed solution containing an oligomer having a terminal chloroformate group 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.

[0045] In producing an oligomer of the dihydric phenol (I), the entire amount of the dihydric phenol (I) used in the method of the present invention may be converted into an oligomer at once, or a part of the oligomer may be added as a post-added monomer as a reaction raw material to the interfacial polycondensation reaction in the subsequent stage. The post-added monomer is added to rapidly proceed with the polycondensation reaction in the subsequent stage, and there is no need to add it if it is not necessary.

[0046] The method for this oligomer formation reaction is not particularly limited, but it is usually preferable to carry out the reaction in a solvent in the presence of an acid binder.

[0047] The proportion of the carbonate ester-forming compound used may be adjusted appropriately in consideration of the stoichiometric ratio (equivalents) of the reaction. When a gaseous carbonate ester-forming compound such as phosgene is used, it is preferable to blow it into the reaction system.

[0048] 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).

[0049] As the solvent, various solvents inert to reactions, such as those used in the production of known polycarbonate resins, 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.

[0050] 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.

[0051] In the present invention, after obtaining a mixed solution containing an oligomer of a dihydric phenol (I) having terminal chloroformate groups in this manner, the mixed solution is stirred while adding 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, 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.

[0052] [ka]

[0053] (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 of 10 to 300. X is a divalent aliphatic group having 2 to 8 carbon atoms.

[0054] When carrying out the interfacial polycondensation reaction, an acid binder may be added as appropriate, taking into account the stoichiometric ratio (equivalents) of the reaction. Examples of acid binders that can be used 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).

[0055] 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.

[0056] In such polymerization reactions, a terminal terminator or a molecular weight modifier is usually used. Examples of terminal terminators 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, and it is of course possible to use two or more compounds in combination.

[0057] To accelerate the polycondensation reaction, a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt may be added.

[0058] 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-hydroxydiphenyl)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 Examples include trisphenols such as {1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and acid chlorides thereof, and among these, 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, with 1,1,1-tris(4-hydroxyphenyl)ethane being 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 any of reduced pressure, normal pressure, and increased pressure, but usually, it can be preferably carried out at normal pressure or about the self-pressure of the reaction system. The reaction temperature is selected from the range of -20 to 50 °C. Since heat is usually generated during polymerization, it is desirable to carry out water cooling or ice cooling. The reaction time varies depending on other conditions such as the reaction temperature and cannot be generally specified, but usually, it is carried out for 0.5 to 10 hours.

[0061] In some cases, the obtained polycarbonate-polydiorganosiloxane copolymer resin is appropriately subjected to physical treatment (such as mixing, fractionation, etc.) and / or chemical treatment (such as polymer reaction, crosslinking treatment, partial decomposition treatment, etc.) to obtain a polycarbonate-polydiorganosiloxane copolymer resin with a desired reduced viscosity [η SP / c].

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

[0063] The average size of the polydiorganosiloxane domain in the polycarbonate-polydiorganosiloxane copolymer resin molded product is preferably in the range of 1 to 60 nm. Such an average size is more preferably 3 to 55 nm, and even more preferably 5 to 50 nm. If it is less than the lower limit of such a suitable range, the impact resistance and flame retardancy are not sufficiently exhibited. If it exceeds the upper limit of such a suitable range, the impact resistance may not be stably exhibited.

[0064] <Component B: Recycled polycarbonate-based resin> The polycarbonate resin composition of the present invention contains a recycled polycarbonate-based resin as component B. Methods for recycling polycarbonate-based resins from used products are described in detail, for example, in JP-A-2000-198116. Raw materials for such recycled polycarbonate-based resins include various glazing materials typified by sound insulation walls, automobile windows, translucent roofing materials, and automobile sunroofs, transparent members such as windshields and automobile headlamp lenses, containers such as water bottles, light guide plates, spectacle lenses, and optical recording media. Further, pulverized products obtained from defective products, sprues, runners, etc. of products or pellets obtained by melting them can also be used. Also, recycled resin pellets of polycarbonate-based resins can be purchased from manufacturers of recycled resins and used.

[0065] The content of component B is 70 to 100 parts by weight, preferably 75 to 100 parts by weight, more preferably 80 to 100 parts by weight, in 100 parts by weight in total of components A and B. The larger the content of component B, the more preferable it is from the viewpoint of environmental protection. If it is less than the lower limit, there is no problem in terms of properties, but the contribution to the social environment becomes small.

[0066] <Component C: Phosphorus-based flame retardant> The polycarbonate resin composition of the present invention contains a phosphorus-based flame retardant as component C. Such phosphorus-based flame retardants include organic phosphorus compounds such as phosphate esters, condensed phosphate esters, and phosphazene compounds, and red phosphorus. Among them, phosphate esters and phosphazenes are preferable. Phosphate esters refer to ester compounds of phosphoric acid and alcohol compounds or phenol compounds. Such phosphate esters and phosphazenes are effective for improving flame retardancy and have a plasticizing effect. Therefore, although there is a decrease in heat resistance, they are advantageous in that they can improve the molding processability of the polycarbonate resin composition of the present invention.

[0067] Specific examples of phosphate esters include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri(2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris(isopropylphenyl) phosphate, tris(phenylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl(2-ethylhexyl) phosphate, di(isopropylphenyl)phenyl phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl acid phosphate, 2- Examples of condensed phosphate esters include methacryloyloxyethyl acid phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate, diethyl phenylphosphonate, resorcinol polyphenyl phosphate, resorcinol poly(di-2,6-xylyl)phosphate, bisphenol A polycresyl phosphate, hydroquinone poly(2,6-xylyl)phosphate, and condensates thereof. Examples of condensed phosphate esters include resorcinol bis(di-2,6-xylyl)phosphate, resorcinol bis(diphenyl phosphate), and bisphenol A bis(diphenyl phosphate).

[0068] Commercially available resorcinol bis(di-2,6-xylyl)phosphate products include "PX-200" manufactured by Daihachi Chemical Industry Co., Ltd. Commercially available resorcinol bis(diphenyl phosphate) products include "CR-733S" manufactured by Daihachi Chemical Industry Co., Ltd. Commercially available bisphenol A bis(diphenyl phosphate) products include "CR-741" manufactured by Daihachi Chemical Industry Co., Ltd.

[0069] Phosphazene compounds can impart flame retardancy to resin compositions by containing phosphorus atoms and nitrogen atoms in the molecule. The phosphazene compound is not particularly limited as long as it is a compound that does not contain a halogen atom and has a phosphazene structure in the molecule. The phosphazene structure referred to here represents a structure represented by the formula: -P(R2)=N- [wherein, R2 is an organic group]. The phosphazene compound is represented by general formulas (4) and (5).

[0070] [Chemical formula] [Chemical formula] (In the formula, X1, X2, X3, and X4 represent a hydrogen atom, a hydroxyl group, an amino group, or an organic group that does not contain a halogen atom. Further, n represents an integer of 3 to 10.)

[0071] In the above general formulas (4) and (5), examples of the organic group that does not contain a halogen atom represented by X1, X2, X3, and X4 include an alkoxy group, a phenyl group, an amino group, an allyl group, and the like.

[0072] Examples of commercially available phosphazene compounds include "FP-100", "FP-110", "FP-110T", etc. manufactured by Fushimi Pharmaceutical Co., Ltd.

[0073] The content of component C is 1 to 25 parts by weight, preferably 2 to 20 parts by weight, and more preferably 3 to 15 parts by weight with respect to a total of 100 parts by weight of components A and B. When the content of component C is less than 1 part by weight, sufficient flame retardancy is not exhibited, and when it exceeds 25 parts by weight, the impact resistance decreases.

[0074] <Component D: A polytetrafluoroethylene-based mixture composed of polytetrafluoroethylene particles obtained by suspension polymerization and a styrene-based organic polymer> The polycarbonate resin composition of the present invention contains, as component D, a PTFE-based mixture comprising polytetrafluoroethylene (hereinafter referred to as PTFE) particles obtained by suspension polymerization and a styrene-based organic polymer. The PTFE-based mixture has an external coating layer composed of a styrene-based organic polymer obtained by copolymerizing a styrene monomer. The coating layer is formed on the surface of the PTFE. Examples of styrene monomers used in the styrene-based organic polymer in the PTFE-based mixture of the present invention include styrenes optionally substituted with one or more groups selected from the group consisting of alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, and halogens, such as styrene, ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, dimethylstyrene, ethylstyrene, para-tert-butylstyrene, methoxystyrene, fluorostyrene, monobromostyrene, dibromostyrene, and tribromostyrene, vinylxylene, and vinylnaphthalene, but are not limited thereto. The styrene monomers can be used alone or in combination of two or more types. Among these, styrene is preferred. The proportion of PTFE in the blend is preferably 35 to 60 wt %, more preferably 40 to 55 wt %, based on 100 wt % of the PTFE blend. Without the coating layer, PTFE aggregation occurs during production, resulting in poor feeder extrusion and making production impossible. Furthermore, if the coating layer is made of a material other than a styrene-based organic polymer, production is possible, but aggregation occurs during recycling, making it impossible to maintain flame retardancy after recycling. The PTFE is particulate, preferably having a particle diameter of 0.1 to 0.6 μm, more preferably 0.3 to 0.5 μm, and even more preferably 0.3 to 0.4 μm. A particle diameter smaller than 0.1 μm results in excellent surface appearance of molded articles, but it is difficult to commercially obtain PTFE with a particle diameter smaller than 0.1 μm. Furthermore, a particle diameter larger than 0.6 μm may result in poor surface appearance of molded articles.

[0075] The PTFE-based mixture in the present invention is produced by the suspension polymerization method according to the following procedure. First, water and branched polytetrafluoroethylene dispersion (solid concentration: 60%) are placed in a reactor, and then, while stirring, styrene monomer and cumene hydroperoxide as a water-soluble initiator are added, and the reaction is carried out at 80 to 90 °C for 9 hours. After the reaction is completed, water is removed by centrifuging for 30 minutes using a centrifuge to obtain a paste-like product. Then, the paste of the product is dried at 80 to 100 °C for 8 hours using a hot air dryer. Thereafter, the dried product is pulverized to obtain the PTFE-based mixture of the present invention. Such a suspension polymerization method does not require the polymerization step by emulsion dispersion in the emulsion polymerization method exemplified in Patent Publication No. 3469391, etc., and thus does not require an emulsifier and electrolyte salts for coagulating and precipitating the latex after polymerization. Further, in the PTFE mixture produced by the emulsion polymerization method, the emulsifier and electrolyte salts in the mixture are likely to be mixed and difficult to remove, so it is difficult to reduce the sodium ions and potassium ions derived from such emulsifier and electrolyte salts. The polytetrafluoroethylene-based mixture used in the present invention is produced by the suspension polymerization method, and since such an emulsifier and electrolyte salts are not used, the contents of sodium ions and potassium ions in the mixture can be reduced. In the PTFE-based mixture obtained by a method other than suspension polymerization, the flame retardancy cannot be maintained after recycling.

[0076] The content of Component D is 0.05 to 4 parts by weight, preferably 0.1 to 3 parts by weight, more preferably 0.2 to 1.5 parts by weight, based on 100 parts by weight in total of Component A and Component B. If the content of Component D is less than 0.05 parts by weight, sufficient flame retardancy is not exhibited. If it exceeds 4 parts by weight, not only does the impact resistance decrease, but the aggregation of PTFE is likely to occur, deteriorating the recyclability.

[0077] <Component E: Impact modifier> The polycarbonate resin composition of the present invention may contain an impact modifier as component E. Such an impact modifier is preferably a graft polymer obtained by graft polymerizing at least one compound, including a (meth)acrylic acid ester compound, onto a rubber selected from the group consisting of butadiene rubber, acrylic rubber, and silicone-acrylic composite rubber. A graft polymer having a core-shell structure is more preferred. A core-shell graft polymer is a graft copolymer in which a rubber component having a glass transition temperature of 10°C or less is copolymerized as a core with one or more monomers selected from (meth)acrylic acid ester compounds, aromatic alkenyl compounds, and vinyl compounds copolymerizable therewith as a shell. Such graft copolymers are expected to improve impact resistance and are advantageous in that they can enhance the mechanical properties of the polycarbonate resin composition of the present invention.

[0078] Examples of rubber components include butadiene rubber, butadiene-acrylic composite rubber, acrylic rubber, silicone-acrylic composite rubber, isobutylene-silicone composite rubber, isoprene rubber, styrene-butadiene rubber, chloroprene rubber, ethylene-propylene rubber, nitrile rubber, ethylene-acrylic rubber, silicone rubber, epichlorohydrin rubber, fluororubber, and those with hydrogen added to the unsaturated bonds. The glass transition temperature of the rubber component is preferably -10°C or lower, more preferably -30°C or lower. For these reasons, butadiene rubber and acrylic silicone-acrylic composite rubber are particularly preferred. Composite rubber refers to rubber obtained by copolymerizing two types of rubber components or rubber polymerized to form an IPN structure in which the components are inseparably intertwined.

[0079] Examples of aromatic vinyl compounds in the vinyl compounds copolymerized with the rubber component as the shell of the core-shell graft polymer include styrene, α-methylstyrene, p-methylstyrene, alkoxystyrene, and halogenated styrene. Examples of acrylic esters include methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, and octyl acrylate. Examples of methacrylic esters include methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, and octyl methacrylate, with methyl methacrylate being particularly preferred. Among these, it is preferable to include methacrylic esters such as methyl methacrylate as an essential component. From the viewpoints of mechanical properties and flame retardancy, it is even more preferable to not include an aromatic vinyl component. More specifically, the methacrylic ester is preferably contained in an amount of 10 wt% or more, more preferably 15 wt% or more, based on 100 wt% of the graft component (or 100 wt% of the shell in the case of a core-shell polymer). Elastic polymers containing a rubber component with a glass transition temperature of 10°C or lower may be produced by any of the following polymerization methods: bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. The copolymerization method may be either single-stage or multi-stage grafting. They may also be a mixture with a copolymer of only the graft component, which is a by-product of production. Polymerization methods include conventional emulsion polymerization, soap-free polymerization using an initiator such as potassium persulfate, seed polymerization, and two-stage swelling polymerization. In suspension polymerization, the aqueous phase and the monomer phase are kept separate and precisely fed into a continuous disperser, with the particle size controlled by the rotation speed of the disperser. In continuous production, the particle size can be controlled by feeding the monomer phase into an aqueous liquid with dispersibility through a small orifice or porous filter with a diameter of several to several tens of micrometers. In the case of core-shell graft polymers, the reaction for both the core and shell may be single-stage or multi-stage.

[0080] The content of component E is preferably 0.01 to 15 parts by weight, more preferably 1 to 10 parts by weight, and still more preferably 2 to 7 parts by weight, based on 100 parts by weight in total of components A and B. If the content of component D is less than 0.01 part by weight, a sufficient impact resistance improvement effect may not be exhibited, and if it exceeds 15 parts by weight, sufficient flame retardancy may not be achieved.

[0081] <Component F: Silicate mineral> The polycarbonate resin composition of the present invention can contain a silicate mineral as component F. Such a silicate mineral is a mineral composed of at least a metal oxide component and a SiO2 component, and orthosilicate, disilicate, cyclic silicate, chain silicate, etc. are suitable. The silicate mineral takes a crystalline state, and the shape of the crystal can take various shapes such as fibrous and plate-like.

[0082] The silicate mineral may be any of a composite oxide, an oxygen acid salt (consisting of an ionic lattice), and a solid solution. Further, the composite oxide may be any of a combination of two or more single oxides and a combination of two or more single oxides and oxygen acid salts. Further, in the solid solution, it may be any of a solid solution of two or more metal oxides and a solid solution of two or more oxygen acid salts. The silicate mineral may be a hydrate. The form of crystal water in the hydrate may be any of those in which it enters as a hydrogen silicate ion as Si-OH, those in which it enters ionically as a hydroxide ion (OH - ) with respect to a metal cation, and those in which it enters as an H2O molecule in the gaps of the structure.

[0083] As the silicate mineral, a synthetic product corresponding to a natural product can also be used. As the synthetic product, silicate minerals obtained from various conventionally known methods, for example, various synthesis methods using solid reaction, hydrothermal reaction, and ultrahigh pressure reaction, etc., can be used.

[0084] Specific examples of silicate minerals in each metal oxide component (MO) include the following: The notation in parentheses indicates the name of a mineral containing such a silicate mineral as a main component, and means that the compound in parentheses can be used as the exemplified metal salt.

[0085] Examples of rocks containing K2O include K2O·SiO2, K2O·4SiO2·H2O, K2O·Al2O3·2SiO2 (kalsilite), K2O·Al2O3·4SiO2 (leucite), and K2O·Al2O3·6SiO2 (orthoclase).

[0086] Materials containing Na2O include Na2O·SiO2 and its hydrates, Na2O·2SiO2, 2Na2O·SiO2, Na2O·4SiO2, Na2O·3SiO2·3H2O, Na2O·Al2O3·2SiO2, Na2O·Al2O3·4SiO2 (jadeite), 2Na2O·3CaO·5SiO2, 3Na2O·2CaO·5SiO2, and Na2O·Al2O3·6SiO2 (albite).

[0087] Examples of rocks containing Li2O include Li2O·SiO2, 2Li2O·SiO2, Li2O·SiO2·H2O, 3Li2O·2SiO2, Li2O·Al2O3·4SiO2 (petalite), Li2O·Al2O3·2SiO2 (eucryptite), and Li2O·Al2O3·4SiO2 (spodumene).

[0088] Examples of materials containing BaO include BaO·SiO2, 2BaO·SiO2, BaO·Al2O3·2SiO2 (celsian), and BaO·TiO2·3SiO2 (bentite).

[0089] Examples of materials containing CaO include 3CaO·SiO2 (alite, a cement clinker mineral), 2CaO·SiO2 (belite, a cement clinker mineral), 2CaO·MgO·2SiO2 (akermanite), 2CaO·Al2O3·SiO2 (gehlenite), a solid solution of akermanite and gehlenite (melilite), CaO·SiO2 (wollastonite (including both α- and β-types)), CaO·MgO·2SiO2 (diopside), CaO·MgO·SiO2 (magnesium olivine), 3CaO·MgO·2SiO2 (merwinite), CaO·Al2O3·2SiO2 (anorthite), 5CaO·6SiO2·5H2O (tobermorite, and others such as 5CaO·6SiO2·9H2O). group hydrates, wollastonite group hydrates such as 2CaO·SiO2·H2O (hillebrandite), xonotlite group hydrates such as 6CaO·6SiO2·H2O (xonotlite), gyrolite group hydrates such as 2CaO·SiO2·2H2O (gyrolite), CaO·Al2O3·2SiO2·H2O (lawsonite), CaO·FeO·2SiO2 (hedengite), 3CaO·2SiO2 (chilcoanite), 3CaO·Al2O3·3SiO2 (grossula), 3CaO·Fe2O3·3SiO2 (andradite), 6CaO·4Al2O3·FeO·SiO2 (pleochroite), as well as clinozoisite, pimerite, allanite, vesuvianite, onoite, scotite, and augite.

[0090] Portland cement is another example of a silicate mineral containing CaO. There are no particular limitations on the type of Portland cement, and any type can be used, including normal, early-strength, ultra-early-strength, moderate-heat, sulfate-resistant, and white. Furthermore, various blended cements, such as blast furnace cement, silica cement, and fly ash cement, can also be used as component F.

[0091] Other silicate minerals containing CaO include blast furnace slag and ferrite.

[0092] Examples of compounds containing ZnO include ZnO·SiO2, 2ZnO·SiO2 (troostite), and 4ZnO·2SiO2·H2O (hemimorphite).

[0093] Examples of materials containing MnO include MnO·SiO2, 2MnO·SiO2, CaO·4MnO·5SiO2 (rhodonite), and cosrite.

[0094] Examples of FeO-containing minerals include FeO·SiO2 (ferrosilite), 2FeO·SiO2 (ferroolivine), 3FeO·Al2O3·3SiO2 (almandine), and 2CaO·5FeO·8SiO2·H2O (tetactinocene).

[0095] Examples of materials that contain CoO include CoO·SiO2 and 2CoO·SiO2.

[0096] Materials containing MgO include MgO·SiO2 (steatite, enstatite), 2MgO·SiO2 (forsterite), 3MgO·Al2O3·3SiO2 (byrope), 2MgO·2Al2O3·5SiO2 (cordierite), 2MgO·3SiO2·5H2O, 3MgO·4SiO2·H2O (talc), 5MgO·8SiO2·9H2O (attapulgite), 4MgO·6SiO2·7H2O (sepiolite), and Examples include 3MgO·2SiO2·2H2O (chrysolite), 5MgO·2CaO·8SiO2·H2O (tremolite), 5MgO·Al2O3·3SiO2·4H2O (chlorite), K2O·6MgO·Al2O3·6SiO2·2H2O (phlogovite), Na2O·3MgO·3Al2O3·8SiO2·H2O (lanthusite), as well as magnesium tourmaline, anthosphite, cummingtonite, vermiculite, and smectite.

[0097] Examples of materials that contain Fe2O3 include Fe2O3·SiO2.

[0098] Examples of materials that contain ZrO2 include ZrO2·SiO2 (zircon) and AZS refractories.

[0099] Examples of materials containing Al2O3 include Al2O3·SiO2 (sillimanite, andalusite, kyanite), 2Al2O3·SiO2, Al2O3·3SiO2, 3Al2O3·2SiO2 (mullite), Al2O3·2SiO2·2H2O (kaolinite), Al2O3·4SiO2·H2O (pyrophyllite), Al2O3·4SiO2·H2O (bentonite), K2O·3Na2O·4Al2O3·8SiO2 (nepheline), K2O·3Al2O3·6SiO2·2H2O (muscovite, sericite), K2O·6MgO·Al2O3·6SiO2·2H2O (phlogovite), as well as various zeolites, fluorphlogopite, and biotite.

[0100] Among the silicate minerals, talc, mica and wollastonite are preferred, and talc is particularly preferred from the viewpoint of flame retardancy and mechanical properties.

[0101] (talc) Talc in the present invention is hydrous magnesium silicate in terms of chemical composition, generally expressed by the chemical formula 4SiO2·3MgO·2H2O. It is usually a scaly particle with a layered structure, and is composed of 56-65% by weight of SiO2, 8-35% by weight of MgO2, and approximately 5% by weight of H2O. Other minor components include 0.03-1.2% by weight of Fe2O3, 0.05-1.5% by weight of Al2O3, 0.05-1.2% by weight of CaO, 0.2% by weight or less of K2O, and 0.2% by weight or less of Na2O. The particle size of the talc is preferably an average particle size measured by the sedimentation method in the range of 0.1-15 μm (more preferably 0.2-12 μm, even more preferably 0.3-10 μm, and particularly preferably 0.5-5 μm). Furthermore, the bulk density is preferably 0.5 (g / cm 3It is particularly preferable to use talc having a particle size of 0.05 mm or more as the raw material. The average particle size of talc refers to the D50 (median diameter of particle size distribution) measured by X-ray transmission, which is one of the liquid phase sedimentation methods. A specific example of an apparatus for performing such measurements is the Sedigraph 5100 manufactured by Micromeritics.

[0102] There are no particular limitations on the method for pulverizing talc from raw ore, and methods such as axial flow milling, annular milling, roll milling, ball milling, jet milling, and container rotation compression shear milling can be used. Furthermore, the talc after pulverization is preferably classified using various classifiers to achieve a uniform particle size distribution. There are no particular limitations on the classifier, and examples include impactor-type inertial force classifiers (such as variable impactors), Coanda effect-based inertial force classifiers (such as elbow jets), and centrifugal field classifiers (such as multi-stage cyclones, microplexes, dispersion separators, AccuCuts, turboclassifiers, turboplexes, micron separators, and super separators). Furthermore, talc is preferably in an agglomerated state for ease of handling, and methods for producing such talc include degassing and compression, and compression using a sizing agent. In particular, the method of degassing and compressing is preferred because it is simple and does not allow unnecessary sizing agent resin components to be mixed into the resin composition of the present invention.

[0103] (mica) Mica with an average particle size of 10 to 100 μm as measured by microtrack laser diffraction is preferably used. More preferably, the average particle size is 20 to 50 μm. Mica with an average particle size of less than 10 μm does not sufficiently improve rigidity, while mica with an average particle size of more than 100 μm does not sufficiently improve rigidity and may significantly reduce mechanical strength, such as impact resistance. Mica with a thickness of 0.01 to 1 μm as measured by electron microscope observation is preferably used. More preferably, the thickness is 0.03 to 0.3 μm. The aspect ratio is preferably 5 to 200, more preferably 10 to 100. Furthermore, muscovite mica is preferably used, and its Mohs hardness is approximately 3. Muscovite mica can achieve higher rigidity and strength than other micas such as phlogopite, thereby achieving a more satisfactory solution to the problems of the present invention. Furthermore, the mica may be produced by either a dry milling method or a wet milling method. Dry grinding is more common and less expensive, while wet grinding is effective for grinding mica into thinner, finer particles, which results in a greater effect of improving the rigidity of the resin composition.

[0104] (Wollastonite) The fiber diameter of wollastonite is preferably 0.1 to 10 μm, more preferably 0.1 to 5 μm, and even more preferably 0.1 to 3 μm. The aspect ratio (average fiber length / average fiber diameter) is preferably 3 or more. The upper limit of the aspect ratio is 30 or less. The fiber diameter is measured by observing the reinforcing filler with an electron microscope, determining the individual fiber diameters, and calculating the number-average fiber diameter from the measured values. An electron microscope is used because it is difficult to accurately measure the size of the target using an optical microscope. The fiber diameter is measured by randomly selecting fillers to be measured from the image obtained by electron microscope observation, measuring the fiber diameter near the center, and calculating the number-average fiber diameter from the obtained measured values. The magnification of the observation is approximately 1000x, and the number of measured fibers is 500 or more (600 or less is preferable for practical purposes). Meanwhile, the average fiber length is measured by observing the filler with an optical microscope, determining the individual lengths, and calculating the number-average fiber length from the measured values. Observation under an optical microscope begins with preparing a sample in which the fillers are dispersed so that they do not overlap too much. Observation is carried out using a 20x objective lens, and the observed image is captured as image data on a CCD camera with approximately 250,000 pixels. The obtained image data is then analyzed using an image analyzer, and the fiber length is calculated using a program that determines the maximum distance between two points on the image data. Under these conditions, the size per pixel corresponds to a length of 1.25 μm, and the number of fibers measured is 500 or more (600 or less is optimal for practical purposes).

[0105] In order to fully reflect the inherent whiteness of the wollastonite of the present invention in the resin composition, it is preferable to use a magnetic separator to remove as much iron as possible from the raw ore and from the equipment worn during the grinding of the raw ore. After such magnetic separator treatment, the iron content in the wollastonite is preferably 0.5% by weight or less, calculated as Fe2O3.

[0106] The silicate mineral (more preferably, mica, talc, or wollastonite) is preferably not surface-treated, but may be surface-treated with various surface treatment agents such as silane coupling agents, higher fatty acid esters, and waxes. Furthermore, it may be granulated into granules using sizing agents such as various resins, higher fatty acid esters, and waxes.

[0107] The content of component F is preferably 0.01 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, and even more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the total of components A and B. If the content of component F is less than 0.01 part by weight, sufficient flame retardancy may not be exhibited, whereas if it exceeds 15 parts by weight, not only will impact resistance decrease but sufficient flame retardancy may also not be exhibited.

[0108] (Other additives) (i) Phosphorus-based stabilizers The polycarbonate resin composition of the present invention may contain a phosphorus-based stabilizer, which is effective in suppressing thermal decomposition during molding and maintaining good impact resistance and flame retardancy.

[0109] Examples of phosphorus-based stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof, as well as tertiary phosphines.

[0110] Specific examples of the phosphite compound include triphenyl phosphite, tris(nonylphenyl)phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, tris(diethylphenyl)phosphite, tris(di-isopropylphenyl)phosphite, and tris(di-n-butylphenyl)phosphite. bis(2,6-di-tert-butylphenyl)pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(2,6-di-tert-butylphenyl)phosphite, distearyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-ethylphenyl)pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, dicyclohexyl pentaerythritol diphosphite, and the like.

[0111] Other phosphite compounds that react with dihydric phenols to form a cyclic structure can also be used, such as 2,2'-methylenebis(4,6-di-tert-butylphenyl)(2,4-di-tert-butylphenyl)phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, 2,2'-methylenebis(4-methyl-6-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, and 2,2'-ethylidenebis(4-methyl-6-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite.

[0112] Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, octadecyl phosphate, etc. Preferred are octadecyl phosphate, triphenyl phosphate, and trimethyl phosphate.

[0113] Examples of phosphonite compounds include tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,3'-biphenylene diphosphonite, and tetrakis(2 ,6-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, bis(2,4-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, bis(2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6-di-n-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, bis(2,6-di-tert-butylphenyl)-3-phenyl-phenylphosphonite, etc. Among these, tetrakis(di-tert-butylphenyl)-biphenylene diphosphonite and bis(di-tert-butylphenyl)-phenyl-phenylphosphonite are preferred, and tetrakis(2,4-di-tert-butylphenyl)-biphenylene diphosphonite and bis(2,4-di-tert-butylphenyl)-phenyl-phenylphosphonite are more preferred. Such a phosphonite compound can be used in combination with the above-mentioned phosphite compound having an aryl group substituted with two or more alkyl groups, and is therefore preferred.

[0114] Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.

[0115] Examples of tertiary phosphines include triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, tri-p-tolylphosphine, trinaphthylphosphine, and diphenylbenzylphosphine. A particularly preferred tertiary phosphine is triphenylphosphine.

[0116] The phosphorus-based stabilizer may be used alone or in combination with two or more kinds. Among the phosphorus-based stabilizers, it is preferable to use them in combination with phosphite compounds and phosphonite compounds.

[0117] The content of the phosphorus-based stabilizer is preferably 0.01 to 1 part by weight, and more preferably 0.02 to 0.9 parts by weight, per 100 parts by weight of the total of Components A and B. If the content is less than 0.01 part by weight, thermal decomposition during molding may not be sufficiently suppressed and no effect on maintaining impact resistance may be observed, whereas if the content exceeds 1 part by weight, thermal decomposition during molding may be promoted, resulting in a decrease in impact resistance.

[0118] (ii) Phenolic stabilizers The polycarbonate resin composition of the present invention may contain a phenolic stabilizer. Examples of phenolic stabilizers generally include hindered phenols, semi-hindered phenols, and less hindered phenol compounds, but hindered phenol compounds are particularly preferred from the viewpoint of providing heat stability to resins including polycarbonate resins and styrene resins.

[0119] Examples of such hindered phenol compounds 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-methylphenylacrylate, 2,6-di-tert-butyl-4-(N,N-dimethylaminomethyl)phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester. esters, 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) alcohol), 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-hydroxyphenyl)propionate] 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'-dithiobis(2,6-di-tert-butylphenol), 4,4'-tri-thiobis(2,6-di-tert-butylphenol), 2,2-thiodiethylene bis-[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'-hexamethylene bis-(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-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 1,3,5-tris2[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-methylphenyl)propionate, triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)acetate, 3,9-bis[2-{3-(3-tert-butyl Examples include tetrakis[methylene-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-2,4,6-tris(3-tert-butyl-4-hydroxy-5-methylbenzyl)benzene, and tris(3-tert-butyl-4-hydroxy-5-methylbenzyl)isocyanurate.

[0120] 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.

[0121] The above phenolic stabilizers can be used alone or in combination of two or more.

[0122] The content of the phenolic stabilizer is preferably 0.01 to 1 part by weight, and more preferably 0.02 to 0.9 parts by weight, per 100 parts by weight of the total of Components A and B. If the content is less than 0.01 part by weight, thermal decomposition during molding may not be sufficiently suppressed and no effect on maintaining impact resistance may be observed, whereas if the content exceeds 1 part by weight, thermal decomposition during molding may be promoted, resulting in a decrease in impact resistance.

[0123] (iii) Mold release agent The polycarbonate resin composition of the present invention may contain a mold release agent to the extent that the effects of the present invention are exhibited in order to improve mold releasability during molding and reduce distortion of molded articles.

[0124] Known release agents can be used. Examples include saturated fatty acid esters, unsaturated fatty acid esters, polyolefin waxes (polyethylene wax, 1-alkene polymers, etc.; those modified with functional group-containing compounds such as acid-modified waxes can also be used), silicone compounds (silicone oils, organosiloxanes, etc.), fluorine compounds (fluorine oils typified by polyfluoroalkyl ethers, etc.), paraffin wax, and beeswax. Among these, fatty acid esters are preferred as release agents.

[0125] Such fatty acid esters are esters of aliphatic alcohols and aliphatic carboxylic acids. Such aliphatic alcohols may be monohydric alcohols or polyhydric alcohols having dihydric or higher hydric groups, and preferably have 3 to 32 carbon atoms, more preferably 5 to 30 carbon atoms. 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.

[0126] 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 the aliphatic carboxylic acid 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, aliphatic carboxylic acids having 14 to 20 carbon atoms are preferred. Among these, saturated aliphatic carboxylic acids are more preferred. Stearic acid and palmitic acid are even more preferred.

[0127] The above-mentioned aliphatic carboxylic acids, such as stearic acid and palmitic acid, are usually produced from natural fats and oils, such as animal fats and oils typified by beef tallow and lard, and vegetable fats and oils typified by palm oil and sunflower oil, and therefore these aliphatic carboxylic acids are usually mixtures containing other carboxylic acid components with different numbers of carbon atoms. Therefore, in the production of the fatty acid ester of the present invention, aliphatic carboxylic acids, particularly stearic acid and palmitic acid, which are produced from such natural fats and oils and are in the form of a mixture containing other carboxylic acid components are preferably used.

[0128] The fatty acid ester may be either a partial ester or a full ester (full ester). However, partial esters usually have a high hydroxyl value, which can easily induce decomposition of the resin at high temperatures, so full esters are more preferred. From the viewpoint of thermal stability, the acid value of such fatty acid esters is preferably 20 or less, more preferably 4 to 20, and even more preferably 4 to 12. The acid value can be substantially 0. In addition, the hydroxyl value of such fatty acid esters is preferably 0.1 to 30, and the iodine value of such fatty acid esters is preferably 10 or less. The iodine value can be substantially 0. These properties can be determined by the method specified in JIS K 0070.

[0129] The above-mentioned release agents may be used alone or in combination of two or more.

[0130] The content of the release agent is preferably 0.01 to 2 parts by weight, and more preferably 0.02 to 1 part by weight, relative to 100 parts by weight of the total of Components A and B. If the content is less than 0.01 part by weight, good release properties may not be achieved, and if it exceeds 2 parts by weight, impact resistance may decrease.

[0131] (iv) ultraviolet absorber The polycarbonate resin composition of the present invention may contain an ultraviolet absorber for the purpose of imparting light resistance. Examples of ultraviolet absorbers include benzophenone-based ultraviolet absorbers, cyclic iminoester-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, and triazine-based ultraviolet absorbers. Among these, benzotriazole-based ultraviolet absorbers and triazine-based ultraviolet absorbers are preferred.

[0132] Benzotriazole-based ultraviolet absorbers include 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, and 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole. Examples of such an ester include 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-4-octoxyphenyl)benzotriazole, 2,2'-methylenebis(4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis(1,3-benzoxazin-4-one), and 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole. Other examples include polymers having a 2-hydroxyphenyl-2H-benzotriazole skeleton, such as a copolymer of 2-(2'-hydroxy-5-methacryloxyethylphenyl)-2H-benzotriazole and a vinyl monomer copolymerizable with said monomer, and a copolymer of 2-(2'-hydroxy-5-acryloxyethylphenyl)-2H-benzotriazole and a vinyl monomer copolymerizable with said monomer.

[0133] Suitable examples of triazine-based UV absorbers include hydroxyphenyltriazine compounds such as 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-methyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-ethyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-propyloxyphenol, and 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-butyloxyphenol.Further examples include compounds in which the phenyl group of the above-mentioned hydroxyphenyltriazine compounds is replaced with a 2,4-dimethylphenyl group, such as 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hexyloxyphenol.

[0134] The above ultraviolet absorbents may be used alone or in combination of two or more kinds.

[0135] (v) Dyes and pigments The polycarbonate resin composition of the present invention contains various dyes and pigments, and can provide molded articles with a variety of designs. By blending a fluorescent brightening 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.

[0136] Examples of fluorescent dyes (including fluorescent brighteners) 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.

[0137] Examples of dyes other than the above 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 good metallic color. Suitable metallic pigments are those having a metal coating or a metal oxide coating on various plate-like fillers.

[0138] (vi) Other resins and elastomers The polycarbonate resin composition of the present invention may contain small amounts of other resins or elastomers as long as the effects of the present invention are exhibited.

[0139] Examples of such other resins include polyester resins such as polyethylene terephthalate resin and 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 epoxy resin.

[0140] Examples of such elastomers include silicone rubber / isobutylene / isoprene rubber, ethylene / propylene rubber, acrylic elastomers, polyester elastomers, and polyamide elastomers.

[0141] (vii) Other additives In addition, the polycarbonate resin composition of the present invention may contain small amounts of known additives in order to impart various functions to the molded article or to improve its properties. These additives may be added in normal amounts as long as they do not impair the object of the present invention.

[0142] Such additives include sliding agents (e.g., PTFE particles), colorants (e.g., pigments and dyes other than the above-mentioned dyes and pigments, such as carbon black), light diffusing agents (e.g., acrylic crosslinked particles, silicone crosslinked particles, ultrathin glass flakes, etc.), inorganic phosphors (e.g., phosphors having aluminate as the host crystal), crystal nucleating agents, radical generators, infrared absorbers (heat ray absorbers), and photochromic agents.

[0143] <Production of Polycarbonate Resin Composition> Any method can be used to produce the polycarbonate resin composition of the present invention, for example, by thoroughly mixing components A to D and optionally other additives using a premixing means such as a V-type blender, a Henschel mixer, a mechanochemical device, or an extrusion mixer, granulating the premix using an extrusion granulator or a briquetting machine as needed, melt-kneading the mixture in a melt kneader such as a vented twin-screw extruder, and then pelletizing the mixture using a pelletizer or other device.

[0144] <Production of molded article obtained by molding polycarbonate resin composition> The polycarbonate resin composition of the present invention can be injection molded from pellets obtained by the above-mentioned method to produce various molded articles. Such injection molding can be carried out not only by conventional cold runner molding methods, but also by hot runners, which enable runnerless molding. In addition to conventional molding methods, other molding methods can be used, including gas-assisted injection molding, injection compression molding, ultra-high-speed injection molding, injection press molding, two-color molding, sandwich molding, in-mold coating molding, insert molding, foam molding (including those using supercritical fluids), rapid heating and cooling mold molding, adiabatic mold molding, in-mold remelt molding, and combinations of these.

[0145] The polycarbonate resin composition of the present invention can also be used in the form of various profile extrusion molded products, sheets, films, etc. by extrusion molding. Sheets and films can also be molded by inflation, calendaring, casting, etc. Furthermore, by subjecting the composition to a specific stretching operation, it can also be molded into heat-shrinkable tubing. The polycarbonate resin composition of the present invention can also be molded into molded articles by rotational molding, blow molding, etc.

[0146] Furthermore, molded articles formed from polycarbonate resin compositions can be subjected to various surface treatments, such as decorative painting, hard coating, water-repellent / oil-repellent coating, hydrophilic coating, ultraviolet absorbing coating, infrared absorbing coating, electromagnetic wave absorbing coating, heat-generating coating, antistatic coating, antistatic coating, conductive coating, and metallizing (plating, chemical vapor deposition (CVD), physical vapor deposition (PVD), thermal spraying, etc.).

[0147] <Flame retardancy> The flammability rating of a test piece (thickness: 1.0 mm) made of the polycarbonate resin composition of the present invention in a vertical flame test in accordance with UL 94 is preferably V-1, and more preferably V-0. If the flammability rating is below V-1, it is difficult to apply the composition to applications requiring high flame retardancy.

[0148] <Impact resistance> The notched Charpy impact strength of the test specimen conforming to ISO179 is 7kJ / m 2 More than 10 kJ / m is preferable. 2 Above this range is more preferable. If the strength is below this preferred range, it is difficult to apply it to various uses, and it is particularly difficult to apply it to housings and the like that require strength. The upper limit of the measured value of the notched Charpy impact strength is not particularly limited except for the upper limit of detection of the measuring instrument, but it is not particularly limited to 100 kJ / m 2 The following performs well:

[0149] <Recyclability> (Flame retardant) The molded article and molded article runners used in the above flame retardancy evaluation are crushed, and the crushed articles are remolded into test pieces (1.0 mm) and subjected to a vertical flame test in accordance with UL 94. The flame retardancy (recyclability) is evaluated with a flammability rating of preferably V-1, and more preferably V-0. If the flammability rating is below V-1, it is difficult to apply the material to applications requiring a high level of flame retardancy.

[0150] (shock resistance) The molded product and molded product runner used in the above impact resistance evaluation are pulverized, and the pulverized product is remolded into test specimens. The notched Charpy impact strength of the test specimens conditioned at 23°C in accordance with ISO 179 is measured, and the impact resistance retention calculated using the following formula is preferably 60% or more, and more preferably 70% or more. If the retention rate is below 60%, it will be difficult to apply the material to various uses. Impact resistance retention rate (%) = [Charpy impact strength after recycling / Charpy impact strength before recycling] x 100 [Example]

[0151] The present invention will be described in more detail below with reference to examples, but these examples are not intended to limit the scope of the present invention. Unless otherwise specified, parts in the examples are parts by weight and % is % by weight. Evaluations were made according to the following methods.

[0152] (Evaluation of Polycarbonate Resin Composition) (1) PTFE dispersibility (productivity) During the extrusion described below, the supply of raw materials from the raw material supply feeder was judged as follows. 〇: No problem ×: Poor dispersion of PTFE causes solidification of raw materials, resulting in production defects (2) Flame retardancy In accordance with the UL 94 vertical flame test established by UL LLC (Underwriters Laboratories Limited Liability Company) in the United States, a flame test was conducted using a 1.0 mm thick molded product (12.5 mm wide, 125 mm long, 1.0 mm thick) prepared using the method described below as the test specimen. Flame retardancy was determined based on the test results and rated as V-0, V-1, V-2, or not V. (3) Impact resistance (notched Charpy impact strength) The notched Charpy impact strength of test pieces (width 10 mm, length 80 mm, thickness 4.0 mm) prepared by the method described below was measured in accordance with ISO179. (4) Recyclability (I) Flame retardant The molded articles and molded article runners used in the above flame retardancy evaluation were crushed, and the crushed articles were remolded into test specimens (width 12.5 mm, length 125 mm, thickness 1.0 mm) under the same conditions, and a vertical combustion test in accordance with UL 94 was carried out. (II) Impact resistance (notched Charpy impact strength) The molded product and molded product runner used in the above impact resistance evaluation were pulverized, and these pulverized products were remolded under the same conditions into test pieces (width 10 mm, length 80 mm, thickness 4.0 mm). The notched Charpy impact strength was measured in accordance with ISO 179, and the impact resistance retention rate was calculated using the following formula. Impact resistance retention rate (%) = [Charpy impact strength after recycling / Charpy impact strength before recycling] x 100

[0153] [Examples 1 to 18, Comparative Examples 1 to 7] Components A through D and other components were uniformly mixed in a V-blender to obtain a mixture according to the composition shown in Tables 1 and 2. The mixture was fed into a 30 mm screw-diameter vented twin-screw extruder (The Japan Steel Works, Ltd.; TEX30α-38.5BW-3V) at the feed port using a scale to adjust the ratio to the desired level. The mixture was melt-kneaded at a cylinder and die temperature of 240–280°C, a screw rotation speed of 200 rpm, a discharge rate of 25 kg / h, and a vent vacuum of 3 kPa. The strands extruded from the die were cooled in a water bath and then cut into pellets using a pelletizer. A portion of the resulting pellets was dried in a hot-air circulating dryer at 80–120°C for 5 hours. Then, molded articles for various evaluations were fabricated using an injection molding machine (Sumitomo Heavy Industries, Ltd.; SE130EV-A) at a cylinder temperature of 240–280°C and a mold temperature of 60°C.

[0154] The evaluation results are shown in Tables 1 and 2. The symbols used for each component in Tables 1 and 2 are as follows: (Component A) A-1: Aromatic polycarbonate resin [Teijin Limited; Panlite L-1225WS (product name), a linear aromatic polycarbonate resin powder with a viscosity-average molecular weight of 20,900 and a repeating skeleton of 2,2-bis(4-hydroxyphenyl)propane] (B component) B-1: Recycled polycarbonate resin [manufactured by Ningbo Asahi Hongyu Technology Co., Ltd.: PC116A (product name)] (C component) C-1: Phosphorus-based flame retardant [manufactured by Daihachi Chemical Industry Co., Ltd.; CR-741 (product name), a phosphoric acid ester whose main component is bisphenol A bis(diphenyl phosphate)] (D component) D-1: Polytetrafluoroethylene mixture [manufactured by Shine Polymer; SN3307PF (product name), a polytetrafluoroethylene mixture obtained by suspension polymerization and consisting of polytetrafluoroethylene particles and styrene-based organic polymers] D-2 (Comparative Example): Polytetrafluoroethylene [manufactured by Daikin Industries, Ltd.; Polyflon MPA FA-500H (product name), polytetrafluoroethylene] D-3 (Comparative Example): Polytetrafluoroethylene mixture [Blendex 449 (trade name), manufactured by Crompton, a polytetrafluoroethylene mixture obtained by emulsion polymerization and consisting of polytetrafluoroethylene particles and a styrene-based organic polymer] D-4 (Comparative Example): Polytetrafluoroethylene mixture [FT-60M (trade name), manufactured by Shokozan Kogyosho Co., Ltd., a polytetrafluoroethylene mixture composed of polytetrafluoroethylene particles obtained by suspension polymerization and silicate minerals] (E component) E-1: Impact modifier [Kaneka Corporation; Kane Ace M-711 (product name), a graft copolymer with a core-shell structure, the core of which is primarily butadiene rubber and the shell of which is primarily methyl methacrylate] E-2: Impact modifier [Kaneka Corporation; Kane Ace M-724 (product name), a graft copolymer with a core-shell structure, the core of which is mainly butadiene rubber and the shell of which is mainly methyl methacrylate and styrene] (F component) F-1: Talc [Victorite TK-RC (product name) manufactured by Shokozan Mining Co., Ltd.] F-2: Mica [Muscovite MC-40 (product name) manufactured by Hayashi Kasei Co., Ltd.] (Other ingredients) STB-1: Phosphorus stabilizer [ADEKA Corporation; Adeka STAB 2112 (product name), tris(2,4-di-tert-butylphenyl) phosphite] STB-2: Phenolic stabilizer [ADEKA Corporation; Adeka STAB AO-50 (product name), octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] Wax: Fatty acid ester-based release agent [NOF Corporation; Unistar H-476-S (product name), pentaerythritol tetrastearate] UVA: ultraviolet absorber [ADEKA CORPORATION; Adeka STAB LA-31 (product name), 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol]

[0155] [Table 1]

[0156] [Table 2]

[0157] Tables 1 and 2 show that by adding a specific blending amount of a phosphorus-based flame retardant and a polytetrafluoroethylene mixture obtained by suspension polymerization, which is composed of polytetrafluoroethylene particles and a styrene-based organic polymer, to a polycarbonate-based resin and a recycled polycarbonate-based resin, a polycarbonate resin composition can be obtained that has excellent dispersibility and flame retardancy of polytetrafluoroethylene when a high proportion of recycled polycarbonate-based resin is used, and that also has excellent recyclability when attempting to reuse molded articles of the resin composition.

Claims

1. A polycarbonate resin composition comprising 100 parts by weight of a total of 0 to 30 parts by weight of (A) a polycarbonate resin (component A) and 100 to 70 parts by weight of (B) a recycled polycarbonate resin (component B), with 1 to 25 parts by weight of (C) a phosphorus-based flame retardant (component C), and 0.05 to 4 parts by weight of (D) a polytetrafluoroethylene mixture (component D) obtained by suspension polymerization and consisting of polytetrafluoroethylene particles and a styrene-based organic polymer.

2. 2. The polycarbonate resin composition according to claim 1, further comprising 0.01 to 15 parts by weight of an impact modifier (E) (Component E) per 100 parts by weight of the total of Components A and B.

3. 3. The polycarbonate resin composition according to claim 1, further comprising 0.01 to 15 parts by weight of a silicate mineral (Component F) per 100 parts by weight of the total of Components A and B.

4. A molded article obtained by molding the resin composition according to claim 1 or 2.

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