Recycled polycarbonate resin composition and molded article made therefrom

Abstract

The present invention provides a recycled polycarbonate resin composition having properties equivalent to those of the original resin composition before recycling, including impact resistance, flame retardancy, and appearance characteristics during molding, as well as molded articles obtained by injection molding therefrom. [Solution] A resin composition containing (A) 100 parts by weight of crushed polycarbonate resin molded product (component A), (B) 1 to 60 parts by weight of polycarbonate resin (component B) having a viscosity-average molecular weight of 17,000 or more, (C) 0.5 to 35 parts by weight of butadiene-based impact modifier (component C) having an alkali metal content of 300 ppm or less, (D) 0.01 to 20 parts by weight of silicate mineral (component D), and (E) 30 parts by weight or less of phosphorus-based flame retardant (component E).

Description

[Technical Field]

[0001] This invention relates to a recycled polycarbonate resin composition having properties equivalent to those of the original polycarbonate resin composition, such as impact resistance, flame retardancy, and appearance during molding, and to a molded article obtained by molding the recycled polycarbonate resin composition. [Background technology]

[0002] Polycarbonate resin is widely used in many applications, including machine parts, automotive parts, office automation equipment such as printers and copiers, and electrical and electronic components, due to its excellent properties such as transparency, impact resistance, heat resistance, dimensional stability, and flame retardancy. In recent years, with the growing awareness of environmental protection, there has been a strong social demand for the recycling of resins, and regulations are also being strengthened. In line with such demands, there is a requirement to use recycled resins, especially in products such as office automation equipment and electrical and electronic components, and the demand for polycarbonate resin compositions with a high proportion of recycled resin is increasing year by year. Furthermore, in recent years, there has been a demand to achieve the original concept of "recycling," that is, to achieve properties in the recycled resin composition that are almost equivalent to those of the original resin composition, thus achieving so-called closed-loop recycling.

[0003] However, recycled resin compositions deteriorate due to hydrolysis and UV exposure, leading to a decrease in properties such as impact resistance and flame retardancy, as well as causing defects in appearance during molding. For this reason, attempts have been made to obtain recycled resin compositions that closely resemble the properties of the original resin composition by mixing an appropriate amount of so-called virgin resin with resin recovered from discarded products. For example, as means of improving the properties of recycled polycarbonate resin, a method has been disclosed in which impact resistance is improved by specifying the ratio of bulk density to true density of crushed thermoplastic resin molded products and adding virgin raw materials (Patent Document 1), and a method has been disclosed in which impact resistance and flame retardancy are improved by adding a drip inhibitor to the recycled polycarbonate resin composition (Patent Documents 2 and 3). However, neither of these methods is sufficient to improve the defects in appearance during molding of the recycled polycarbonate resin composition, and currently, the impact resistance, flame retardancy, and appearance during molding of recycled polycarbonate resin compositions do not reach the properties that the original resin composition originally possessed. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2002-265798 [Patent Document 2] Japanese Patent Publication No. 2005-289047 [Patent Document 3] Japanese Patent Publication No. 2013-163813 [Overview of the project] [Problems that the invention aims to solve]

[0005] In view of the above, the object of the present invention is to provide a recycled polycarbonate resin composition having properties equivalent to the impact resistance, flame retardancy, and appearance characteristics during molding of the resin composition before recycling, and a molded article made therefrom. [Means for solving the problem]

[0006] As a result of intensive studies to solve the above problems, the present inventors have found that the above object can be achieved by adding specific amounts of a polycarbonate resin, a butadiene-based impact modifier having an alkali metal content of 300 ppm or less, a silicate mineral, and a phosphorus-based flame retardant to crushed polycarbonate resin molded products, and have completed the present invention.

[0007] That is, the present invention is as follows. (Configuration 1) (A) 1 to 60 parts by weight of a polycarbonate-based resin (Component B) having a viscosity-average molecular weight of 17,000 or more, (C) 0.5 to 35 parts by weight of a butadiene-based impact modifier (Component C) having an alkali metal content of 300 ppm or less, (D) 0.01 to 20 parts by weight of a silicate mineral (Component D), and (E) 30 parts by weight or less of a phosphorus-based flame retardant (Component E) are contained per 100 parts by weight of the crushed polycarbonate resin molded product (Component A). A recycled polycarbonate resin composition characterized by the above. (Configuration 2) The recycled polycarbonate resin composition according to Configuration 1, wherein the viscosity-average molecular weight of the polycarbonate resin in Component A is 80% or more of the viscosity-average molecular weight of the polycarbonate resin in Component A which is a virgin raw material. (Configuration 3) The recycled polycarbonate resin composition according to Configuration 1 or 2, characterized by containing 0.01 to 2 parts by weight of an anti-dripping agent (Component F) per 100 parts by weight of Component A. (Configuration 4) The recycled polycarbonate resin composition according to any one of Configurations 1 to 3, characterized by containing 0.01 to 1 part by weight of at least one stabilizer (Component G) selected from the group consisting of a phosphorus-based stabilizer and a phenol-based stabilizer per 100 parts by weight of Component A. (Configuration 5) A molded product obtained by injection molding the recycled polycarbonate resin composition according to any one of Configurations 1 to 4.

Effects of the Invention

[0008] The recycled polycarbonate resin composition of the present invention has properties equivalent to those of the polycarbonate resin composition before recycling, such as impact resistance, flame retardancy, and appearance characteristics during molding processing. It is widely useful not only in OA and EE applications but also in various fields such as housing equipment applications, building materials applications, consumer goods applications, infrastructure equipment applications, automotive applications, outdoor equipment applications, and others. Therefore, the industrial effect of the present invention is extremely significant for the realization of a sustainable society.

Embodiments for Carrying Out the Invention

[0009] Hereinafter, the details of the present invention will be described.

[0010] <Component A: Crushed Polycarbonate Resin Molded Product> Component A of the present invention is preferably recycled material of molded articles made of polycarbonate resin composition, that is, (i) recycled material of molded articles that have been used in the market as part of a product, and have been collected after the product's lifespan has ended by consumers, etc., and (ii) recycled material of molded articles that have been processed at least once from virgin pellets, such as defective products, sprues, runners, etc. that are generated incidentally in the molding process before they come to market, as well as defective products in the product manufacturing process and molded articles that are no longer needed as inventory. The recycled material is usually collected from products while sorting the plastic components into similar parts, and then crushed using a crusher. Examples of crushers include compression crushers (such as roll crushers), impact crushers (such as impact crushers and hammer mills), cutting or shearing crushers (such as cutter mills, reciprocating crushers, and low-speed rotary crushers (such as twin-shaft shearing crushers)), impact shearing crushers (such as shredders), and various fine crushers (such as ball mills, disc mills, pin mills, hammer mills, turbo mills, and jet mills). Among the above, cutting or shearing crushers are preferred because they can be supplied with molded products directly, have excellent crushing efficiency, and can accommodate the required particle size. Among these, low-speed rotary crushers are preferred because they have an appropriate bulk density even for highly tough exterior molded products, making it easier to obtain desirable crushed material. Any type of low-speed rotary crusher, such as single-shaft, twin-shaft, or triple-shaft, can be used.

[0011] It is also important to maintain the condition of the rotating and stationary blades of the crusher in good condition. If the rotating or stationary blades are worn, the deformation of the fracture surface tends to increase in highly tough materials. Such deformation unnecessarily increases the bulk density, which is undesirable in the manufacturing process. The ratio of bulk density to true density of the crushed material (bulk density / true density) preferably has a lower limit of 0.3 (particularly preferably 0.38) and an upper limit of 0.5 (particularly preferably 0.49).

[0012] The shape and size of the recycled material are not particularly limited, but from the standpoint of ease of supplying to the extruder and handling, the particle size of the crushed material (corresponding to the longest particle diameter) is preferably in the range of 1 to 30 mm, more preferably 1 to 15 mm, even more preferably 1.5 to 12 mm, and particularly preferably 2 to 10 mm. The particle size of such crushed material can be measured according to the standard sieving method. Furthermore, crushed material of the above particle size can be obtained by installing a screen with a mesh size close to the desired particle size in the crusher.

[0013] When molded products are coated with printed coatings, seals, labels, decorative coatings, conductive coatings, conductive plating, and metal vapor deposition, both pulverized materials with and without these coatings can be used. The present invention improves the effectiveness of recycling by not strictly requiring the removal of these coatings. When removing such printed coatings or platings, methods include rolling between two rolls, contact with heated and pressurized water, various solvents, acidic and alkaline aqueous solutions, mechanically scraping off the removed portion, irradiating with ultrasound, and blasting. These methods can also be used in combination.

[0014] The polycarbonate resin composition used for molding molded products may be an alloy composition of polycarbonate resin, which is the main component, with other resins such as styrene resins (ABS resin, AS resin, etc.), aromatic polyester resins (polyethylene terephthalate resin (PET resin), polybutylene terephthalate resin (PBT resin), etc.), polyphenylene sulfide resin (PPS resin), polyphenylene ether (PPE resin), cyclohexanedimethanol copolymer polyethylene terephthalate resin (so-called PET-G resin), polyethylene naphthalate resin and polybutylene naphthalate resin, etc.), polymethyl methacrylate resin (PMMA resin), cyclic polyolefin resin, polycaprolactone resin, and polyolefin resins (polyethylene resin, ethylene-(α-olefin) copolymer resin, polypropylene resin and propylene-(α-olefin) copolymer resin). The recycled polycarbonate resin composition may also contain flame retardants, plasticizers, stabilizers, mold release agents, fillers, and colorants.

[0015] The ratio of the viscosity-average molecular weight of the polycarbonate resin in component A to the viscosity-average molecular weight of the polycarbonate resin in the virgin raw material component A (viscosity-average molecular weight retention rate) is preferably 80% or more, and more preferably 85% or more. If the viscosity-average molecular weight retention rate is less than 80%, impact resistance may decrease and flame retardancy may also deteriorate. There is no particular upper limit specified for the viscosity-average molecular weight retention rate, but it is preferably 98% or less. The viscosity-average molecular weight retention rate is calculated by the following formula. Viscosity-average molecular weight retention rate (%) = [Viscosity-average molecular weight of polycarbonate resin in component A / Viscosity-average molecular weight of polycarbonate resin in component A (virgin raw material)] × 100 The viscosity average molecular weight of the polycarbonate resin in Component A and the polycarbonate resin in the virgin raw material of Component A is calculated as follows. That is, Component A or Component A which is the virgin raw material is mixed with 20 to 30 times its weight of methylene chloride to dissolve the soluble components in the component. Next, such soluble components are collected by celite filtration, and then the solvent in the obtained solution is removed. The solid after solvent removal is dried sufficiently to obtain a solid of the component soluble in methylene chloride. Next, the specific viscosity (η SP ) is determined at 20 °C from a solution prepared by dissolving 0.7 g of the solid in 100 ml of methylene chloride using an Ostwald viscometer, Specific viscosity (η SP )=(t - t0) / t0 [t0 is the dropping seconds of methylene chloride, t is the dropping seconds of the sample solution] From the obtained specific viscosity (η SP ), the viscosity average molecular weight M is calculated by 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

[0016] <Component B: Polycarbonate resin> The recycled polycarbonate resin composition of the present invention contains a polycarbonate resin having a viscosity average molecular weight of 17,000 or more as Component B. The polycarbonate resin used in the present invention is obtained by reacting a dihydric phenol with a carbonate precursor. Examples of the reaction method include interfacial polymerization, melt transesterification, solid-phase transesterification of a carbonate prepolymer, and ring-opening polymerization of a cyclic carbonate compound.

[0017] Typical examples of divalent phenols used here include hydroquinone, resorcinol, 4,4'-biphenol, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane (commonly known as bisphenol A), 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxyphenyl)pentane, and 4,4'-(p-phenyl Examples include bis(4-hydroxyphenyl)diphenol, 4,4'-(m-phenylenediisopropylidene)diphenol, 1,1-bis(4-hydroxyphenyl)-4-isopropylcyclohexane, bis(4-hydroxyphenyl)oxide, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)ketone, bis(4-hydroxyphenyl)ester, bis(4-hydroxy-3-methylphenyl)sulfide, 9,9-bis(4-hydroxyphenyl)fluorene, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene. Preferred divalent phenols are bis(4-hydroxyphenyl)alkanes, among which bisphenol A is particularly preferred and widely used in terms of impact resistance.

[0018] In this invention, in addition to bisphenol A-based polycarbonate resins, which are general-purpose polycarbonate resins, it is also possible to use special polycarbonate resins manufactured using other divalent phenols as component A. For example, polycarbonate resins (homopolymers or copolymers) using 4,4'-(m-phenylenediisopropylidene)diphenol (hereinafter sometimes abbreviated as "BPM"), 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as "Bis-TMC"), 9,9-bis(4-hydroxyphenyl)fluorene, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (hereinafter sometimes abbreviated as "BCF") as some or all of the divalent phenol components are suitable for applications where dimensional changes due to water absorption and morphological stability are particularly demanding. These divalent phenols other than BPA are preferably used in an amount of 5 mol% or more, particularly 10 mol% or more, of the total divalent phenol components constituting the polycarbonate resin. In particular, when high rigidity and better hydrolysis resistance are required, the copolymer polycarbonate resins of (1) to (3) below are especially preferred. (1) A copolymer polycarbonate resin in which, of 100 mol% of the divalent phenol component constituting the polycarbonate resin, BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, even more preferably 45 to 65 mol%) and BCF is 20 to 80 mol% (more preferably 25 to 60 mol%, even more preferably 35 to 55 mol%). (2) A copolymer polycarbonate resin in which, of 100 mol% of the divalent phenol component constituting the polycarbonate resin, BPA is 10 to 95 mol% (more preferably 50 to 90 mol%, even more preferably 60 to 85 mol%) and BCF is 5 to 90 mol% (more preferably 10 to 50 mol%, even more preferably 15 to 40 mol%). (3) A copolymer polycarbonate resin in which, of 100 mol% of the divalent phenol component constituting the polycarbonate resin, BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, even more preferably 45 to 65 mol%) and Bis-TMC is 20 to 80 mol% (more preferably 25 to 60 mol%, even more preferably 35 to 55 mol%).

[0019] These special polycarbonate resins may be used individually or mixed in appropriate combinations of two or more types. They can also be mixed with commonly used bisphenol A type polycarbonate resins. The manufacturing methods and properties of these special polycarbonate resins are described in detail in, for example, Japanese Patent Publication No. 6-172508, Japanese Patent Publication No. 8-27370, Japanese Patent Publication No. 2001-55435, and Japanese Patent Publication No. 2002-117580.

[0020] Furthermore, among the various polycarbonate resins mentioned above, those whose copolymerization composition and other properties have been adjusted to bring the water absorption rate and Tg (glass transition temperature) within the following ranges exhibit excellent hydrolysis resistance of the polymer itself, as well as significantly superior low warping after molding. Therefore, they are particularly suitable for fields requiring morphological stability. (i) A polycarbonate resin having a water absorption rate of 0.05 to 0.15%, preferably 0.06 to 0.13%, and a Tg of 120 to 180°C, or (ii) A polycarbonate resin having a Tg of 160 to 250°C, preferably 170 to 230°C, and a water absorption rate of 0.10 to 0.30%, preferably 0.13 to 0.30%, more preferably 0.14 to 0.27%.

[0021] Here, the water absorption rate of the polycarbonate resin was measured using a disc-shaped test piece with a diameter of 45 mm and a thickness of 3.0 mm, after immersion in water at 23°C for 24 hours in accordance with ISO 62-1980. The glass transition temperature (Tg) was determined by differential scanning calorimeter (DSC) measurement in accordance with JIS K7121.

[0022] Carbonyl halides, diester carbonates, or haloformates are used as carbonate precursors, specifically including phosgene, diphenyl carbonate, or dihaloformates of divalent phenols.

[0023] When producing a polycarbonate resin by interfacial polymerization of the divalent phenol and the carbonate precursor, a catalyst, an end-terminating agent, an antioxidant to prevent oxidation of the divalent phenol, etc., may be used as needed. The polycarbonate resin of the present invention includes a branched polycarbonate resin copolymerized with a trifunctional or polyfunctional aromatic compound, a polyester carbonate resin copolymerized with an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid, a copolymerized polycarbonate resin copolymerized with a bifunctional alcohol (including alicyclic), and a polyester carbonate resin copolymerized with both such bifunctional carboxylic acid and bifunctional alcohol. Furthermore, a mixture of two or more of the obtained polycarbonate resins may also be used.

[0024] The branched polycarbonate resin can impart properties such as drip prevention to the recycled polycarbonate resin composition of the present invention. Examples of trifunctional or polyfunctional aromatic compounds used in such branched polycarbonate resins include phloroglucin, phloroglucid, or 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-2, 2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 4-{4-[1,1-bis(4- Examples include trisphenols such as hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acid chlorides, among which 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred.

[0025] In branched polycarbonate resins, the structural units derived from polyfunctional aromatic compounds are preferably 0.01 to 1 mol%, more preferably 0.05 to 0.9 mol%, and even more preferably 0.05 to 0.8 mol%, of the total 100 mol% of structural units derived from divalent phenols and those derived from such polyfunctional aromatic compounds. Furthermore, especially in the case of melt transesterification, branched structural units may be generated as a side reaction, but the amount of such branched structural units is also preferably 0.001 to 1 mol%, more preferably 0.005 to 0.9 mol%, and even more preferably 0.01 to 0.8 mol%, of the total 100 mol% of structural units derived from divalent phenols. 1It can be calculated by 1H-NMR measurement.

[0026] Among aliphatic difunctional carboxylic acids, α,ω-dicarboxylic acids are preferred. Examples of aliphatic difunctional carboxylic acids include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanediic acid), dodecanediic acid, tetradecanediic acid, octadecanediic acid, and eicosanedioic acid, as well as alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. As for difunctional alcohols, alicyclic diols are more preferred, with examples including cyclohexanedimethanol, cyclohexanediol, and tricyclodecanedimethanol.

[0027] The reaction methods used to produce the polycarbonate resin of the present invention, such as interfacial polymerization, molten transesterification, solid-phase transesterification of carbonate prepolymers, and ring-opening polymerization of cyclic carbonate compounds, are well-known methods described in various literatures and patent publications.

[0028] The viscosity-average molecular weight of the polycarbonate resin of the present invention is 17,000 or more, preferably 18,000 or more, more preferably 20,000 or more, and even more preferably 22,000 to 30,000. If the viscosity-average molecular weight is less than 17,000, sufficient impact resistance will not be achieved.

[0029] A more preferred embodiment is a polycarbonate resin (component B-1) in which component B consists of a polycarbonate resin with a viscosity-average molecular weight of 70,000 to 300,000 (component B-1) and a polycarbonate resin with a viscosity-average molecular weight of 10,000 to 30,000 (component B-1), and the viscosity-average molecular weight of the polycarbonate resin (component B-1) is 17,000 to 30,000 (hereinafter sometimes referred to as "high molecular weight component-containing polycarbonate resin").

[0030] In such a high molecular weight component-containing polycarbonate resin (component B-1), the molecular weight of component B-1 is preferably 70,000 to 200,000, more preferably 80,000 to 200,000, even more preferably 100,000 to 200,000, and particularly preferably 100,000 to 160,000. The molecular weight of component B-2 is preferably 10,000 to 25,000, more preferably 11,000 to 24,000, even more preferably 12,000 to 24,000, and particularly preferably 12,000 to 23,000.

[0031] A polycarbonate resin containing high molecular weight components (component B-1) can be obtained by mixing component B-1-1 and component B-1-2 in various proportions and adjusting them to satisfy a predetermined molecular weight range. Preferably, component B-1-1 is 2 to 40% by weight of component B-1 out of 100% by weight of component B-1, more preferably 3 to 30% by weight of component B-1-1, even more preferably 4 to 20% by weight of component B-1-1, and particularly preferably 5 to 20% by weight of component B-1-1.

[0032] Furthermore, methods for preparing component B-1 include (1) a method of independently polymerizing component B-1-1 and component B-1-2 and mixing them; (2) a method of producing a polycarbonate resin that exhibits multiple polymer peaks in a molecular weight distribution chart by GPC method within the same system, as exemplified by the method shown in Japanese Patent Application Publication No. 5-306336, and producing such a polycarbonate resin to satisfy the conditions for component B-1 of the present invention; and (3) a method of mixing the polycarbonate resin obtained by such a production method (production method of (2)) with separately produced component B-1-1 and / or component B-1-2.

[0033] A polycarbonate-polydiorganosiloxane copolymer resin can also be used as the polycarbonate-based resin of the present invention. The polycarbonate-polydiorganosiloxane copolymer resin is preferably a copolymer resin prepared by copolymerizing a divalent phenol represented by the following general formula (1) and a hydroxyaryl-terminated polydiorganosiloxane represented by the following general formula (3).

[0034] [Chemical formula]

[0035] [In the above general formula (1), R 1 and R 2 each independently represent 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 carboxyl group. When there are a plurality of them, they may be the same or different. e and f are each an integer of 1 to 4, and W is at least one group selected from the group consisting of a single bond or a group represented by the following general formula (2).]

[0036] [Chemical formula]

[0037] [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 represent 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 20Each of these independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. If there are multiple groups, they may be the same or different. g is an integer from 1 to 10, and h is an integer from 4 to 7.

[0038] [ka]

[0039] [In the above general formula (3), R 3 , R 4 , R 5 , R 6 , R 7 and R 8 Each of these is independently a hydrogen atom, a C1-C12 alkyl group, or a C6-C12 substituted or unsubstituted aryl group, R 9 and R 10 Each of the following is independently a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, and an alkoxy group with 1 to 10 carbon atoms, where p is a natural number, q is 0 or a natural number, and p+q is a natural number between 10 and 300. X is a divalent aliphatic group with 2 to 8 carbon atoms.

[0040] Examples of divalent phenols (I) represented by general formula (1) include 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxy-3,3'-biphenyl)propane, 2,2- Bis(4-hydroxy-3-isopropylphenyl)propane, 2,2-bis(3-t-butyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, 2,2-bis(3-bromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane, bis(4-H 1,1-bis(4-hydroxyphenyl)fluorene, 2,2-diphenylmethane, 3,1-bis(4-hydroxyphenyl)cyclohexane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 2,2'- Dimethyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 2,2'-diphenyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfide, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,Examples include 4-bis(4-hydroxyphenyl)cyclohexane, 1,3-bis(4-hydroxyphenyl)cyclohexane, 4,8-bis(4-hydroxyphenyl)tricyclo[5.2.1.02,6]decane, 4,4'-(1,3-adamantanediyl)diphenol, and 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane. Among these, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-sulfonyldiphenol, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, and 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene are preferred, with 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane (BPZ), 4,4'-sulfonyldiphenol, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene being particularly preferred. Among these, 2,2-bis(4-hydroxyphenyl)propane, which has excellent strength and good durability, is the most suitable. These may be used individually or in combination of two or more.

[0041] As the hydroxyaryl-terminated polydiorganosiloxane represented by the above general formula (3), the following compounds are preferably used, for example.

[0042] [ka]

[0043] Hydroxyaryl-terminated polydiorganosiloxanes (II) can be easily produced by hydrosiliculation reaction of olefinic unsaturated carbon-carbon bonded phenols, preferably vinylphenol, 2-allylphenol, isopropenylphenol, and 2-methoxy-4-allylphenol, to the ends of a polysiloxane chain having a predetermined degree of polymerization. Among these, (2-allylphenol)-terminated polydiorganosiloxanes and (2-methoxy-4-allylphenol)-terminated polydiorganosiloxanes are preferred, and (2-allylphenol)-terminated polydimethylsiloxanes and (2-methoxy-4-allylphenol)-terminated polydimethylsiloxanes are particularly preferred. Hydroxyaryl-terminated polydiorganosiloxanes (II) preferably have a molecular weight distribution (Mw / Mn) of 3 or less. Furthermore, in order to exhibit excellent low outgassing and low-temperature impact resistance during high-temperature molding, such a molecular weight distribution (Mw / Mn) is more preferably 2.5 or less, and even more preferably 2 or less. If the upper limit of this suitable range is exceeded, the amount of outgassing during high-temperature molding increases, and the low-temperature impact resistance may be poor.

[0044] Furthermore, to achieve high impact resistance, the degree of diorganosiloxane polymerization (p+q) of the hydroxyaryl-terminated polydiorganosiloxane(II) is appropriately set to 10-300. This degree of diorganosiloxane polymerization (p+q) is preferably 10-200, more preferably 12-150, and even more preferably 14-100. Below the lower limit of this preferred range, the impact resistance characteristic of polycarbonate-polydiorganosiloxane copolymers is not effectively exhibited, and above the upper limit of this preferred range, appearance defects appear.

[0045] The polydiorganosiloxane content in the total weight of the polycarbonate-polydiorganosiloxane copolymer resin is preferably 0.1 to 50% by weight. More preferably, the polydiorganosiloxane content is 0.5 to 30% by weight, and even more preferably 1 to 20% by weight. Above the lower limit of this preferred range, excellent impact resistance and flame retardancy are obtained, and below the upper limit of this preferred range, a stable appearance less affected by molding conditions is easily obtained. The degree of polydiorganosiloxane polymerization and polydiorganosiloxane content are: 1 It can be calculated by 1H-NMR measurement.

[0046] In the present invention, only one hydroxyaryl-terminated polydiorganosiloxane(II) may be used, or two or more may be used. Furthermore, to the extent that it does not interfere with the present invention, other comonomers other than the divalent phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II) may be used in combination in an amount of 10% by weight or less relative to the total weight of the copolymer.

[0047] In the present invention, a mixed solution containing an oligomer having terminal chloroformate groups is prepared in advance by the reaction of divalent phenol(I) and a carbonate ester-forming compound in a mixture of a water-insoluble organic solvent and an alkaline aqueous solution.

[0048] In producing the divalent phenol(I) oligomer, the entire amount of divalent phenol(I) used in the method of the present invention may be converted into an oligomer at once, or a portion of it may be added as a reaction material to the subsequent interfacial polycondensation reaction as a post-added monomer. The post-added monomer is added to expedite the subsequent polycondensation reaction, and it is not necessary to add it if it is not needed. The method of this oligomer formation reaction is not particularly limited, but it is generally preferable to carry it out in a solvent in the presence of an acid binder.

[0049] The proportion of ester-forming compounds used can be adjusted as appropriate, taking into account the stoichiometric ratio (equivalent) of the reaction. Furthermore, when using gaseous ester-forming compounds such as phosgene, a suitable method is to bubble them into the reaction system.

[0050] Examples of acid binders include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, or mixtures thereof. The proportion of acid binder used should be determined appropriately, taking into account the stoichiometric ratio (equivalents) of the reaction, as described above. Specifically, it is preferable to use 2 equivalents or a slightly excess amount of acid binder relative to the number of moles of divalent phenol(I) used to form the oligomer (usually 1 mole corresponds to 2 equivalents).

[0051] As the aforementioned solvent, various reaction-inert solvents, such as those used in the production of known polycarbonate resins, can be used individually or as a mixed solvent. Typical examples include hydrocarbon solvents such as xylene, and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. Halogenated hydrocarbon solvents such as methylene chloride are particularly preferred.

[0052] There are no particular restrictions on the reaction pressure for oligomer formation; it can be atmospheric pressure, pressurized pressure, or reduced pressure, but it is usually advantageous to carry out the reaction under atmospheric pressure. The reaction temperature is selected from the range of -20 to 50°C, and since polymerization is often exothermic, water cooling or ice cooling is desirable. The reaction time depends on other conditions and cannot be specified in general, but it is usually carried out in 0.2 to 10 hours. The pH range for the oligomer formation reaction is the same as for known interfacial reaction conditions, and the pH is always adjusted to 10 or higher.

[0053] In this invention, a mixed solution containing an oligomer of divalent phenol (I) having terminal chloroformate groups is obtained, and while stirring the mixed solution, a hydroxyaryl-terminated polydiorganosiloxane (II) represented by general formula (3), which has been highly purified to a molecular weight distribution (Mw / Mn) of 3 or less, is added to the divalent phenol (I), and the hydroxyaryl-terminated polydiorganosiloxane (II) and the oligomer are subjected to interfacial polycondensation to obtain a polycarbonate-polydiorganosiloxane copolymer.

[0054] [ka]

[0055] (In the above general formula (3), R 3 , R 4 , R 5 , R 6 , R 7 and R 8 Each of these is independently a hydrogen atom, a C1-C12 alkyl group, or a C6-C12 substituted or unsubstituted aryl group, R 9 and R 10 Each of the following is independently a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, and an alkoxy group with 1 to 10 carbon atoms, where p is a natural number, q is 0 or a natural number, and p+q is a natural number between 10 and 300. X is a divalent aliphatic group with 2 to 8 carbon atoms.

[0056] When carrying out an interfacial polycondensation reaction, an acid binder may be added as appropriate, taking into consideration the stoichiometric ratio (equivalent) of the reaction. Examples of acid binders include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, or mixtures thereof. Specifically, when adding a portion of the hydroxyaryl-terminated polydiorganosiloxane(II) or divalent phenol(I) as described above as a post-added monomer to this reaction step, it is preferable to use 2 equivalents or an excess amount of alkali relative to the total number of moles of the post-added divalent phenol(I) and hydroxyaryl-terminated polydiorganosiloxane(II) (usually 1 mole corresponds to 2 equivalents).

[0057] The polycondensation reaction between the divalent phenol (I) oligomer and the hydroxyaryl-terminated polydiorganosiloxane (II) is carried out by vigorously stirring the above mixture.

[0058] In such polymerization reactions, end-terminating agents or molecular weight modifiers are commonly used. Examples of end-terminating agents include compounds having a monovalent phenolic hydroxyl group, such as ordinary phenols, p-tert-butylphenol, p-cumylphenol, and tribromophenol, as well as long-chain alkylphenols, aliphatic carboxylic acid chlorides, aliphatic carboxylic acids, alkyl hydroxybenzoates, hydroxyphenylalkylates, and alkyl etherphenols. The amount used is in the range of 100 to 0.5 moles, preferably 50 to 2 moles, per 100 moles of all divalent phenolic compounds used, and it is naturally possible to use two or more compounds in combination.

[0059] To accelerate the polycondensation reaction, a catalyst such as a tertiary amine like triethylamine or a quaternary ammonium salt may be added. The reaction time for such polymerization is preferably 30 minutes or more, and more preferably 50 minutes or more. Optionally, a small amount of antioxidant such as sodium sulfite or hydrosulfide may be added.

[0060] Branching agents can be used in combination with the above-mentioned divalent phenolic compounds to form branched polycarbonate-polydiorganosiloxanes. Examples of trifunctional or polyfunctional aromatic compounds used in such branched polycarbonate-polydiorganosiloxane copolymer resins include phloroglucin, phloroglucid, or 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-2, 2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, and 4-{4-[1 Examples include trisphenols such as 1-bis(4-hydroxyphenyl)ethyl]benzene-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acid chlorides, among which 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred. The proportion of polyfunctional compounds in the branched polycarbonate-polydiorganosiloxane copolymer resin is preferably 0.001 to 1 mol%, more preferably 0.005 to 0.9 mol%, even more preferably 0.01 to 0.8 mol%, and particularly preferably 0.05 to 0.4 mol%, of the total amount of the polycarbonate-polydiorganosiloxane copolymer resin. 1 It can be calculated by 1H-NMR measurement.

[0061] 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 at about the self-pressure of the reaction system. The reaction temperature is selected from the range of -20 to 50 °C. Since heat is often generated during polymerization, it is desirable to perform 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.

[0062] 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].

[0063] The obtained reaction product (crude product) can be recovered as a polycarbonate-polydiorganosiloxane copolymer resin with a desired purity (degree of purification) by performing various post-treatments such as known separation and purification methods.

[0064] The average size of the polydiorganosiloxane domains 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, and if it exceeds the upper limit of such a suitable range, the impact resistance may not be stably exhibited.

[0065] The content of component B is 1 to 60 parts by weight, preferably 3 to 55 parts by weight, and more preferably 5 to 50 parts by weight, based on 100 parts by weight of component A. If the content of component B is less than 1 part by weight, sufficient impact resistance is not exhibited. If it exceeds 60 parts by weight, there are no problems in terms of properties, but the contribution to the social environment becomes small.

[0066] <Component C: Butadiene-based impact modifier> The polycarbonate resin composition for reproduction of the present invention contains a butadiene-based impact modifier having an alkali metal content of 300 ppm or less as component C. The butadiene-based impact modifier is preferably at least one resin selected from the group consisting of an ABS resin, an MBS resin, and an MB resin from the viewpoints of impact resistance and flame retardancy.

[0067] The alkali metal content in the butadiene-based impact modifier is 300 ppm or less, preferably 200 ppm or less, more preferably 100 ppm or less, and still more preferably 75 ppm or less. When the alkali metal exceeds 300 ppm, the flame retardancy does not appear and the appearance during molding processing also deteriorates. The lower limit of the content is not particularly limited, but it is preferably 0.01 ppm or more.

[0068] The alkali metal content is determined by adding 10 ml of nitric acid to 0.1 g of the butadiene-based impact modifier, decomposing it by microwave heating, diluting it to 25 ml with ultrapure water, and measuring it with an inductively coupled plasma optical emission spectrometer (ICP-AES) conforming to JIS K0116.

[0069] <ABS resin> The ABS resin used in this invention is a mixture of a thermoplastic graft copolymer obtained by graft polymerizing a diene-based rubber component with a vinyl cyanide compound and an aromatic vinyl compound, and a copolymer of a vinyl cyanide compound and an aromatic vinyl compound. As the diene-based rubber component that forms this ABS resin, for example, rubber with a glass transition temperature of -30°C or lower, such as polybutadiene, polyisoprene, and styrene-butadiene copolymer, is used, and its proportion is preferably 5 to 80% by weight, more preferably 8 to 50% by weight, and particularly preferably 10 to 30% by weight, of 100% by weight of the ABS resin component. Acrylonitrile is particularly preferred as the vinyl cyanide compound grafted onto the diene-based rubber component. Styrene and α-methylstyrene are particularly preferred as the aromatic vinyl compound grafted onto the diene-based rubber component. The proportion of the component grafted onto the diene-based rubber component is preferably 95 to 20% by weight, and particularly preferably 50 to 90% by weight, of 100% by weight of the ABS resin component. Furthermore, it is preferable that the vinyl cyanide compound accounts for 5 to 50% by weight and the aromatic vinyl compound for 95 to 50% by weight, based on a total amount of 100% by weight of the vinyl cyanide compound and aromatic vinyl compound. In addition, maleic anhydride, N-substituted maleimide, etc., can be mixed and used as part of the components grafted onto the above diene-based rubber component, and it is preferable that their content is 15% by weight or less of the ABS resin component. Furthermore, various conventionally known initiators, chain transfer agents, emulsifiers, etc., can be used in the reaction as needed.

[0070] In the ABS resin used in the present invention, the rubber particle diameter is preferably 0.1 to 5.0 μm, more preferably 0.15 to 1.5 μm, and particularly preferably 0.2 to 0.8 μm. The distribution of such rubber particle diameters can be either a single distribution or one with two or more peaks. Furthermore, in terms of morphology, the rubber particles may form a single phase, or they may have a salami structure due to the inclusion of an occluded phase around the rubber particles.

[0071] It has long been well known that an ABS resin contains a vinyl cyanide compound and an aromatic vinyl compound that are not grafted to a diene rubber component, and the ABS resin of the present invention may also contain free polymer components generated during such polymerization. The reduced viscosity of a copolymer composed of such free vinyl cyanide compound and aromatic vinyl compound preferably has a reduced viscosity (30 ° C) determined by the method described above of 0.2 to 1.0 dl / g, more preferably 0.3 to 0.7 dl / g.

[0072] Also, the ratio of the grafted vinyl cyanide compound and aromatic vinyl compound is preferably 20 to 200% in terms of grafting rate (weight%) with respect to the diene rubber component, more preferably 20 to 70%.

[0073] Such an ABS resin may be produced by any of bulk polymerization, suspension polymerization, and emulsion polymerization methods, but those obtained by bulk polymerization are particularly preferred. Further, as such bulk polymerization methods, typically, the continuous bulk polymerization method (so-called Toray method) described in Chemical Engineering, Vol. 48, No. 6, p. 415 (1984), and the continuous bulk polymerization method (so-called Mitsui Toatsu method) described in Chemical Engineering, Vol. 53, No. 6, p. 423 (1989) are exemplified. Any ABS resin can be suitably used as the ABS resin of the present invention. Also, the copolymerization method may be carried out by copolymerization in one step or in multiple steps. Further, a blend of a vinyl compound polymer obtained by separately copolymerizing an aromatic vinyl compound and a vinyl cyanide component with the ABS resin obtained by such a production method can also be preferably used.

[0074] <MB Resin and MBS Resin> The MB resin and MBS resin used in this invention are methyl methacrylate-butadiene copolymer and methyl methacrylate-butadiene-styrene copolymer, respectively. Such copolymers are graft polymers, and graft polymers having a core-shell structure are more preferred. The methyl methacrylate content in the MBS resin is preferably 10% by weight or more, and more preferably 15% by weight or more, per 100% by weight of the graft component (or per 100% by weight of the shell in the case of a core-shell polymer). In a core-shell graft polymer, the particle diameter of the core is preferably 240 to 300 nm in weight-average particle diameter, more preferably 250 to 290 nm, and even more preferably 260 to 280 nm. Better impact strength may be achieved in the range of 240 to 300 nm. Furthermore, a bidispersion type particle size distribution with two peaks is desirable, and a bidispersion type with two peaks around 100 nm and 300 nm is particularly preferred, and better impact strength may be achieved than a monodispersion type with a single peak.

[0075] MB resins and MBS resins may be manufactured using any of the following polymerization methods: bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization. The copolymerization method may be single-stage grafting or multi-stage grafting. They may also be mixtures of copolymers consisting only of graft components produced as by-products during manufacturing. In addition to the general emulsion polymerization method, other polymerization methods include soap-free polymerization using initiators such as potassium persulfate, seed polymerization, and two-stage swelling polymerization. Furthermore, in suspension polymerization, methods may be used in which the aqueous phase and monomer phase are held separately and accurately supplied to a continuous disperser, with the particle size controlled by the rotation speed of the disperser. In continuous manufacturing methods, the monomer phase may be supplied through a small-diameter orifice or porous filter with a diameter of several to tens of micrometers in a dispersible aqueous liquid to control the particle size. In the case of core-shell type graft polymers, the reaction may be single-stage or multi-stage for both the core and shell.

[0076] The content of Component C is 0.5 to 35 parts by weight, preferably 1 to 30 parts by weight, more preferably 2 to 25 parts by weight, based on 100 parts by weight of Component A. When the content of Component C is less than 0.5 parts by weight, impact resistance is not exhibited, and when it exceeds 35 parts by weight, the flame retardancy decreases.

[0077] <Component D: Silicate mineral> The recycled polycarbonate resin composition of the present invention contains a silicate mineral as Component D. 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.

[0078] 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 combination of two or more single oxides and any 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 the crystal water in the hydrate may be any of those in which it enters as hydrogen silicate ions as Si-OH, those in which it enters ionically as hydroxide ions (OH - ) with respect to metal cations, and those in which it enters as H2O molecules in the gaps of the structure.

[0079] 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, such as various synthetic methods using solid reaction, hydrothermal reaction, and ultrahigh pressure reaction, can be used.

[0080] Specific examples of the silicate mineral in each metal oxide component (MO) are as follows. Here, the notation in parentheses is the name of a mineral or the like having such a silicate mineral as the main component, and it means that the compound in parentheses can be used as the exemplified metal salt.

[0081] Examples of materials containing K2O include K2O·SiO2, K2O·4SiO2·H2O, K2O·Al2O3·2SiO2 (calcilite), K2O·Al2O3·4SiO2 (white oresite), and K2O·Al2O3·6SiO2 (orthoclase).

[0082] Examples of substances containing Na2O include Na2O·SiO2, its hydrate, 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).

[0083] Examples of substances 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).

[0084] Examples of substances containing BaO include BaO·SiO2, 2BaO·SiO2, BaO·Al2O3·2SiO2 (cerucyan), and BaO·TiO2·3SiO2 (bentite).

[0085] Minerals containing CaO include 3CaO·SiO2 (alite, a cement clinker mineral), 2CaO·SiO2 (belite, a cement clinker mineral), 2CaO·MgO·2SiO2 (okermanitine), 2CaO·Al2O3·SiO2 (gehlenite), solid solutions of okermanitine and gehlenite (merilite), CaO·SiO2 (wolllastonite (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), and tobermorite. Examples include loop hydrates, wollastonite group hydrates such as 2CaO·SiO2·H2O (hillbrandite), xonotlite group hydrates such as 6CaO·6SiO2·H2O (xonotlite), gyrolite group hydrates such as 2CaO·SiO2·2H2O (gyrolite), lawsonite (CaO·Al2O3·2SiO2·H2O), hedenkiite (CaO·FeO·2SiO2), chilcoanite (3CaO·2SiO2), grossula (3CaO·Al2O3·3SiO2), andradite (3CaO·Fe2O3·3SiO2), pleochroite (6CaO·4Al2O3·FeO·SiO2), as well as clinozoisite, rhodochroite, celandine, vesuvianite, onoite, scoutite, and augite.

[0086] Furthermore, Portland cement can be cited as a silicate mineral containing CaO as a component. The type of Portland cement is not particularly limited; any type can be used, including ordinary, rapid-hardening, very rapid-hardening, moderate-heat, sulfate-resistant, and white cements. Additionally, various blended cements, such as blast furnace cement, silica cement, and fly ash cement, can also be used as component D. Other silicate minerals containing CaO include blast furnace slag and ferrite.

[0087] Examples of materials containing ZnO include ZnO·SiO2, 2ZnO·SiO2 (trostite), and 4ZnO·2SiO2·H2O (hemipolarite).

[0088] Examples of substances containing MnO include MnO·SiO2, 2MnO·SiO2, CaO·4MnO·5SiO2 (rhodonite), and causerite.

[0089] Examples of materials containing FeO include FeO·SiO2 (ferrosilite), 2FeO·SiO2 (iron olivine), 3FeO·Al2O3·3SiO2 (almandine), and 2CaO·5FeO·8SiO2·H2O (tetucinoseite).

[0090] Examples of substances containing CoO include CoO·SiO2 and 2CoO·SiO2.

[0091] MgO-containing materials 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 (atapulgite), and 4MgO·6SiO2·7H2O (sepiolite). Examples include 3MgO·2SiO2·2H2O (chrysolite), 5MgO·2CaO·8SiO2·H2O (persimmonite), 5MgO·Al2O3·3SiO2·4H2O (chlorite), K2O·6MgO·Al2O3·6SiO2·2H2O (phlogovite), Na2O·3MgO·3Al2O3·8SiO2·H2O (lanseneite), as well as magnesium tourmaline, orthosene, cumingtonite, vermiculite, smectite, etc.

[0092] Examples of substances containing Fe2O3 as a component include Fe2O3·SiO2.

[0093] Examples of materials containing ZrO2 include ZrO2·SiO2 (zircon) and AZS refractories.

[0094] 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 (neissite), K2O·3Al2O3·6SiO2·2H2O (muscovite, sericite), K2O·6MgO·Al2O3·6SiO2·2H2O (phlogovite), as well as various zeolites, fluorphlogopite, and biotite.

[0095] Among the silicate minerals mentioned above, talc, mica, and wollastonite are preferred, with talc being particularly preferred from the viewpoint of maintaining impact resistance.

[0096] (talc) In this invention, talc is chemically composed of hydrated magnesium silicate, generally represented by the chemical formula 4SiO2·3MgO·2H2O, and typically consists of flake-like particles with a layered structure. Its composition is approximately 56-65% by weight of SiO2, 28-35% by weight of MgO, and about 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% or less by weight of K2O, and 0.2% or less by weight of Na2O. The particle size of the talc is preferably 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) as measured by the sedimentation method. Furthermore, the bulk density is 0.5 g / cm³. 3It is particularly preferable to use talc of a certain size or larger as the raw material. The average particle size of talc is defined as D50 (median diameter of the particle size distribution) measured by X-ray transmission, one of the liquid-phase sedimentation methods. A specific example of an instrument for performing such a measurement is the Sedigraph 5100 manufactured by Micromeristics.

[0097] Furthermore, there are no particular restrictions on the method used to crush talc from its raw material, and methods such as axial flow milling, annular milling, roll milling, ball milling, jet milling, and container-rotating compression shear milling can be used. In addition, the crushed talc is preferably classified using various classifiers to ensure a uniform particle size distribution. There are no particular restrictions on the classifiers, 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, AccuCut, turboclassifiers, turboplexes, micron separators, and super separators). Furthermore, the talc is preferably in an aggregated state for ease of handling, and methods for achieving this include degassing and compression, and compression using a sizing agent. The degassing and compression method is particularly preferable because it is simple and does not involve mixing unnecessary sizing agent resin components into the recycled polycarbonate resin composition of the present invention.

[0098] (Mica) Preferably, mica with an average particle size of 10 to 100 μm, as measured by microtrac laser diffraction, can be used. More preferably, mica with an average particle size of 20 to 50 μm. If the average particle size of the mica is less than 10 μm, the improvement effect on rigidity may not be sufficient, and even if it exceeds 100 μm, the improvement in rigidity may not be sufficient, and there may be a significant decrease in mechanical strength such as impact properties. Preferably, mica with a thickness of 0.01 to 1 μm, as measured by observation with an electron microscope, can be used. More preferably, the thickness is 0.03 to 0.3 μm. The aspect ratio can preferably be 5 to 200, more preferably 10 to 100. Furthermore, muscovite mica is preferred for use, and its Mohs hardness is approximately 3. Compared to other mica such as phlovite, muscovite mica can achieve higher rigidity and strength, and solves the problems of the present invention at a better level. Furthermore, the mica may be manufactured by either a dry grinding method or a wet grinding method. While dry grinding is less expensive and more common, wet grinding is effective in grinding mica into thinner and finer particles, resulting in a greater improvement in the rigidity of recycled polycarbonate resin compositions.

[0099] (Wallastnite) The fiber diameter of the wollastonite is preferably 0.1 to 10 μm, more preferably 0.1 to 5 μm, and even more preferably 0.1 to 3 μm. Furthermore, the aspect ratio (average fiber length / average fiber diameter) is preferably 3 or higher. The upper limit of the aspect ratio is 30 or less. Here, the fiber diameter is determined by observing the reinforcing filler with an electron microscope, determining the diameter of each individual fiber, and calculating the number-average fiber diameter from these measurements. An electron microscope is used because it is difficult to accurately measure the size of the target level with an optical microscope. To determine the fiber diameter, randomly select fillers to be measured from the image obtained by electron microscope observation, measure the fiber diameter near the center, and calculate the number-average fiber diameter from the obtained measurements. The observation magnification is approximately 1000x, and the number of measurements is 500 or more (600 or less is preferable for practical purposes). On the other hand, the average fiber length is measured by observing the filler with an optical microscope, determining the length of each individual fiber, and calculating the number-average fiber length from these measurements. Observation using an optical microscope begins with preparing a sample in which the fillers are dispersed so that they do not overlap too much. The observation is performed under conditions of a 20x objective lens, and the observed image is captured as image data in a CCD camera with approximately 250,000 pixels. The obtained image data is then analyzed using an image analysis device, and the fiber length is calculated using a program that determines the maximum distance between two points in the image data. Under these conditions, the size of each pixel corresponds to a length of 1.25 μm, and the measurement is performed with 500 or more fibers (600 or fewer is preferable for practical purposes).

[0100] In order to fully reflect the inherent whiteness of the wollastonite of the present invention in the recycled polycarbonate resin composition, it is preferable to remove as much iron as possible from the raw ore and from the iron mixed in due to wear of the equipment when crushing the raw ore using a magnetic separator. It is preferable that the iron content in the wollastonite after such magnetic separator treatment is 0.5% by weight or less, converted to Fe2O3.

[0101] The silicate minerals (more preferably mica, talc, wollastonite) are preferably not surface-treated, but may be surface-treated with various surface-treating agents such as silane coupling agents, higher fatty acid esters, and waxes. Further, it may be granulated with a flocculant such as various resins, higher fatty acid esters, and waxes to be in a granular form.

[0102] The content of Component D is 0.01 to 20 parts by weight, preferably 0.2 to 15 parts by weight, and more preferably 0.4 to 10 parts by weight with respect to 100 parts by weight of Component A. When the content of Component D is less than 0.01 part by weight, sufficient flame retardancy is not exhibited and the appearance during molding processing deteriorates, and when it exceeds 20 parts by weight, the impact resistance deteriorates.

[0103] <Component E: Phosphorus-based flame retardant> The recycled polycarbonate resin composition of the present invention preferably contains a phosphorus-based flame retardant as Component E. Such phosphorus-based flame retardants include organic phosphorus compounds such as phosphate esters, condensed phosphate esters, phosphazene compounds, and red phosphorus, among which phosphate esters and phosphazenes are preferable. Phosphate esters refer to ester compounds of phosphoric acid and alcohol compounds or phenolic compounds. Such phosphate esters and phosphazenes are effective in improving flame retardancy and have a plasticizing effect, and although there is a decrease in heat resistance, they are advantageous in that they can improve the molding processability of the recycled polycarbonate resin composition of the present invention.

[0104] 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).

[0105] A commercially available product of resorcinol bis(di-2,6-xylyl) phosphate is "PX-200" manufactured by Daihachi Chemical Industry Co., Ltd. A commercially available product of resorcinol bis(diphenyl phosphate) is "CR-733S" manufactured by Daihachi Chemical Industry Co., Ltd. A commercially available product of bisphenol A bis(diphenyl phosphate) is "CR-741" manufactured by Daihachi Chemical Industry Co., Ltd.

[0106] Phosphazene compounds can impart flame retardancy to a recycled polycarbonate resin composition 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).

[0107]

Chemical formula

[0108]

Chemical formula

[0109] (In the formula, X1, X2, X3, and X4 represent hydrogen, a hydroxyl group, an amino group, or an organic group not containing a halogen atom. Further, n represents an integer of 3 to 10). In the above general formulas (4) and (5), examples of the organic group not containing 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.

[0110] Commercially available phosphazene compounds include "FP-100", "FP-110", "FP-110T", etc. manufactured by Fushimi Pharmaceutical Co., Ltd.

[0111] The content of the E component is 30 parts by weight or less, preferably 25 parts by weight or less, more preferably 20 parts by weight or less, based on 100 parts by weight of the A component. When the content of the E component exceeds 30 parts by weight, the impact resistance decreases. Although the lower limit of the content is not particularly limited, it is preferably 3 parts by weight or more.

[0112] <F component: anti-dripping agent> The recycled polycarbonate resin composition of the present invention may contain a drip inhibitor as component F. Examples of such drip inhibitors include fluorine-containing polymers having fibril-forming ability, such as polytetrafluoroethylene, tetrafluoroethylene copolymers (e.g., tetrafluoroethylene / hexafluoropropylene copolymer, etc.), partially fluorinated polymers as described in U.S. Patent No. 4,379,910, and polycarbonate resins produced from fluorinated diphenols. Among these, polytetrafluoroethylene (hereinafter sometimes referred to as PTFE) is preferred.

[0113] PTFE with fibril-forming ability has an extremely high molecular weight and tends to bond with other PTFE materials to form fibers under external forces such as shear force. Its molecular weight, calculated from the standard specific gravity, is 1 million to 10 million, preferably 2 million to 9 million. Such PTFE can be used in solid form as well as aqueous dispersion form. Furthermore, to improve dispersibility in resins and to obtain even better flame retardancy and mechanical properties, it is also possible to use PTFE mixtures in mixed form with other resins.

[0114] Examples of commercially available PTFE products possessing such fibril-forming ability include Daikin Industries, Ltd.'s "Polyflon MPA FA series (FA-500H and FA-5601, etc.)". Representative examples of commercially available aqueous dispersions of PTFE include Daikin Industries, Ltd.'s "Polyflon PTFE D series (D-111 and D-210C, etc.)".

[0115] As for PTFE in mixed form, (1) a method of mixing an aqueous dispersion of PTFE with an aqueous dispersion or solution of an organic polymer and co-precipitating to obtain a co-aggregated mixture (methods described in Japanese Patent Publication No. 60-258263, Japanese Patent Publication No. 63-154744, etc.), (2) a method of mixing an aqueous dispersion of PTFE with dried organic polymer particles (method described in Japanese Patent Publication No. 4-272957), (3) a method of uniformly mixing an aqueous dispersion of PTFE with an organic polymer particle solution and separating each medium from the mixture. (1) A method of removing the organic polymer in an aqueous dispersion of PTFE (as described in Japanese Patent Publication No. 06-220210, Japanese Patent Publication No. 08-188653, etc.), (2) a method of polymerizing monomers that form an organic polymer in an aqueous dispersion of PTFE (as described in Japanese Patent Publication No. 9-95583), and (3) a method of uniformly mixing an aqueous dispersion of PTFE and an organic polymer dispersion, further polymerizing vinyl monomers in the mixed dispersion, and then obtaining a mixture (as described in Japanese Patent Publication No. 11-29679, etc.) can be used. Examples of commercially available PTFE in these mixed forms include "Metablen A series (A-3750 and A-3800)" manufactured by Mitsubishi Chemical Corporation.

[0116] In the mixed form, the proportion of PTFE is preferably 1 to 60% by weight, and more preferably 5 to 55% by weight, of 100% by weight of the PTFE mixture. When the proportion of PTFE is within this range, good dispersibility of PTFE can sometimes be achieved. Note that the proportion of component F above indicates the net amount of drip inhibitor, and in the case of PTFE in mixed form, it indicates the net amount of PTFE.

[0117] Furthermore, examples of styrene monomers used in the organic polymers used in the polytetrafluoroethylene-based mixtures of the present invention include, but are not limited to, styrenes that may be substituted with one or more groups selected from the group consisting of C1-C6 alkyl groups, C1-C6 alkoxy groups, and halogens, such as ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, dimethylstyrene, ethylstyrene, para-tert-butylstyrene, methoxystyrene, fluorostyrene, monobromostyrene, dibromostyrene, and tribromostyrene, vinylxylene, and vinylnaphthalene. The styrene monomers can be used individually or in combination of two or more types.

[0118] The acrylic monomer used in the organic polymer used in the polytetrafluoroethylene mixture in the present invention includes a substituted (meth)acrylate derivative. Specifically, the acrylic monomer may be a (meth)acrylate derivative substituted with one or more groups selected from the group consisting of C1-C20 alkyl groups, C3-C8 cycloalkyl groups, aryl groups, and glycidyl groups, for example, (meth)acrylonitrile, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl ( Examples of acrylic monomers include, but are not limited to, meth)acrylate, cyclohexyl(meth)acrylate, octyl(meth)acrylate, dodecyl(meth)acrylate, phenyl(meth)acrylate, benzyl(meth)acrylate, and glycidyl(meth)acrylate, maleimides which may be substituted with C1-C6 alkyl groups or aryl groups, such as maleimide, N-methyl-maleimide, and N-phenyl-maleimide, maleic acid, phthalic acid, and itaconic acid. The acrylic monomers can be used individually or in combination of two or more types. Among these, (meth)acrylonitrile is preferred.

[0119] The amount of acrylic monomer-derived units in the organic polymer used in the coating layer is preferably 8 to 11 parts by weight, more preferably 8 to 10 parts by weight, and even more preferably 8 to 9 parts by weight, per 100 parts by weight of styrene monomer-derived units. If the amount of acrylic monomer-derived units is less than 8 parts by weight, the coating strength may decrease, and if it is more than 11 parts by weight, the surface appearance of the molded product may deteriorate.

[0120] The polytetrafluoroethylene-based mixture in the present invention preferably has a residual moisture content of 0.5% by weight or less, more preferably 0.2 to 0.4% by weight, and even more preferably 0.1 to 0.3% by weight. A residual moisture content greater than 0.5% by weight may adversely affect flame retardancy.

[0121] The manufacturing process for the polytetrafluoroethylene mixture in the present invention includes a step of forming a coating layer on the outside of branched polytetrafluoroethylene containing one or more monomers selected from the group consisting of styrene monomers and acrylic monomers in the presence of an initiator. Furthermore, it is preferable to include a step of drying after the coating layer formation step so that the residual moisture content is 0.5% by weight or less, preferably 0.2 to 0.4% by weight, and more preferably 0.1 to 0.3% by weight. The drying step can be carried out using, for example, an art-known method such as hot air drying or vacuum drying.

[0122] The initiator used in the polytetrafluoroethylene mixture of the present invention can be any initiator used in polymerization reactions of styrene-based and / or acrylic monomers without limitation. Examples of such initiators include, but are not limited to, cumyl hydroperoxide, di-tert-butyl peroxide, benzoyl peroxide, hydrogen peroxide, and potassium peroxide. One or more of the above initiators can be used in the polytetrafluoroethylene mixture of the present invention depending on the reaction conditions. The amount of the initiator can be freely selected within a range that takes into account the amount of polytetrafluoroethylene and the type / amount of monomers, and it is preferable to use 0.15 to 0.25 parts by weight based on the amount of the total composition.

[0123] The polytetrafluoroethylene-based mixture used in this invention was produced by suspension polymerization according to the following procedure.

[0124] First, water and branched polytetrafluoroethylene dispersion (solid concentration: 60%, polytetrafluoroethylene particle size: 0.15-0.3 μm) were added to a reactor. Acrylic monomer, styrene monomer, and cumene hydroperoxide as a water-soluble initiator were added while stirring, and the reaction was carried out at 80-90°C for 9 hours. After the reaction was complete, water was removed by centrifugation for 30 minutes to obtain a paste-like product. The paste was then dried in a hot air dryer at 80-100°C for 8 hours. The dried product was then pulverized to obtain the polytetrafluoroethylene-based mixture of the present invention.

[0125] This suspension polymerization method does not require the emulsion dispersion polymerization step exemplified in emulsion polymerization methods such as Patent No. 3469391, and therefore does not require emulsifiers or electrolyte salts for coagulating and precipitating the polymerized latex. Furthermore, in polytetrafluoroethylene mixtures produced by emulsion polymerization, emulsifiers and electrolyte salts tend to be mixed in the mixture and are difficult to remove, making it difficult to reduce the sodium and potassium ions derived from such emulsifiers and electrolyte salts. Since the polytetrafluoroethylene mixture used in the present invention is produced by suspension polymerization, such emulsifiers and electrolyte salts are not used, thus reducing the sodium and potassium ion content in the mixture and improving thermal stability and hydrolysis resistance.

[0126] Furthermore, in the present invention, coated branched PTFE can be used as a drip-preventing agent. Coated branched PTFE is a polytetrafluoroethylene mixture consisting of branched polytetrafluoroethylene particles and an organic polymer, and has a coating layer on the outside of the branched polytetrafluoroethylene consisting of an organic polymer, preferably a polymer containing styrene monomer-derived units and / or acrylic monomer-derived units. The coating layer is formed on the surface of the branched polytetrafluoroethylene. It is also preferable that the coating layer contains a copolymer of styrene monomers and acrylic monomers.

[0127] The polytetrafluoroethylene contained in the coated branched PTFE is branched polytetrafluoroethylene. When the contained polytetrafluoroethylene is not branched polytetrafluoroethylene, the dripping prevention effect when the addition of polytetrafluoroethylene is small becomes insufficient. The branched polytetrafluoroethylene is in the form of particles, preferably having a particle size 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. When the particle size is smaller than 0.1 μm, the surface appearance of the molded product is excellent, but it is difficult to commercially obtain polytetrafluoroethylene having a particle size smaller than 0.1 μm. Also, when the particle size is larger than 0.6 μm, the surface appearance of the molded product may deteriorate. The number average molecular weight of the polytetrafluoroethylene used in the present invention is 1×10 4 ~1×10 7 is preferable, more preferably 2×10 6 ~9×10 6 and generally, polytetrafluoroethylene with a higher molecular weight is more preferable in terms of stability. Either the form of powder or dispersion can be used. The content of the branched polytetrafluoroethylene in the coated branched PTFE is preferably 20 to 60 parts by weight, more preferably 40 to 55 parts by weight, even more preferably 47 to 53 parts by weight, particularly preferably 48 to 52 parts by weight, and most preferably 49 to 51 parts by weight, based on 100 parts by weight of the total weight of the coated branched PTFE. When the proportion of the branched polytetrafluoroethylene is within such a range, good dispersibility of the branched polytetrafluoroethylene may be achieved.

[0128] The content of the F component is preferably 0.01 to 2 parts by weight, more preferably 0.1 to 1.5 parts by weight, and even more preferably 0.3 to 1 part by weight, based on 100 parts by weight of the A component. When the content of the F component is less than 0.01 part by weight, sufficient flame retardancy may not be obtained, and when it exceeds 2 parts by weight, the impact resistance may decrease.

[0129] <G component: at least one stabilizer selected from the group consisting of a phosphorus-based stabilizer and a phenolic stabilizer> The recycled polycarbonate resin composition of the present invention may contain, as component G, at least one stabilizer selected from the group consisting of phosphorus-based stabilizers and phenol-based stabilizers.

[0130] (Phosphorus stabilizer) Examples of phosphorus-based stabilizers include phosphorous acid, phosphoric acid, phosphonic acid, phosphonic acid and their esters, as well as tertiary phosphines. Specifically, examples of phosphite compounds 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-iso-propylphenyl) phosphite, and tris(di-n-butylphenyl) phosphite. Examples include 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, phenylbisphenol A pentaerythritol diphosphite, bis(nonylphenyl) pentaerythritol diphosphite, and dicyclohexyl pentaerythritol diphosphite.

[0131] Furthermore, other phosphite compounds that react with divalent phenols to form cyclic structures can also be used. Examples include 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.

[0132] Examples of phosphate compounds include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenylcresyl phosphate, diphenylmonoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, and diisopropyl phosphate. Triphenyl phosphate and trimethyl phosphate are preferred.

[0133] Examples of phosphonite compounds include tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylenediphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylenediphosphonite, tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylenediphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,4'-biphenylenediphosphonite, tetrakis(2 Examples include ,6-di-tert-butylphenyl)-3,3'-biphenylenediphosphonite, 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, and bis(2,6-di-tert-butylphenyl)-3-phenyl-phenylphosphonite. Among these, tetrakis(di-tert-butylphenyl)-biphenylenediphosphonite and bis(di-tert-butylphenyl)-phenyl-phenylphosphonite are preferred, and tetrakis(2,4-di-tert-butylphenyl)-biphenylenediphosphonite and bis(2,4-di-tert-butylphenyl)-phenyl-phenylphosphonite are more preferred. Such phosphonite compounds can be used in combination with phosphite compounds having aryl groups substituted with two or more alkyl groups, and this is preferable.

[0134] Examples of phosphonate compounds include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.

[0135] 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.

[0136] The phosphorus-based stabilizers described above may be a mixture of two or more types, not just one. Among the phosphorus-based stabilizers, combination use with phosphite compounds and phosphonite compounds is preferred.

[0137] (Phenol-based stabilizers) Phenolic stabilizers generally include hindered phenols, semi-hindered phenols, and less-hindered phenol compounds. However, hindered phenol compounds are particularly preferred for providing heat-stable formulations to resins containing polycarbonate resins and styrene resins.

[0138] Examples of such hindered phenol compounds include α-tocopherol, butylhydroxytoluene, cinapyl alcohol, vitamin E, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, 2,6-di-tert-butyl-4-(N,N-dimethylaminomethyl)phenol, and 3,5-di-tert-butyl-4-hydroxybenzylphosphonatediethyl Luester, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-methylenebis(2,6-di-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-dimethylene-bis(6-α-methyl-benzyl-p-cresol), 2,2'-ethylidene-bis(4,6-di-tert-butylphenol), 2,2'-butylidene-bis(4-methyl-6-tert-butylphenol 4,4'-Butylidenebis(3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], bis[2-tert-butyl-4-methyl6-(3-tert-butyl-5-methyl-2-hydroxybenzyl)phenyl]terephthalate, 3,9-bis{2-[3-(3-tert-butyl-4-hydroxyphenyl] [C-5-methylphenyl)propionyloxy]-1,1,-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, 4,4'-thiobis(6-tert-butyl-m-cresol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-thiobis(4-methyl-6-tert-butylphenol), bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, 4,4'-di-thiobis(2,6-di-tert-butylphenol), 4,4'-tri-thiobis(2,6-di-tert-butylphenol), 2,2-thiodiethylenebis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine, N,N'-hexamethylenebis-(3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, 1,1, 3-Tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-tert-butyl-4-hydroxyphenyl)isocyanurate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 1,3,5-tris-2[3 (3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl isocyanurate, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)acetate, 3,9-bis[2-{3-(3-tert- Examples include tetraxyl-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.

[0139] 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. The above-mentioned phenolic stabilizers can be used individually or in combination of two or more types.

[0140] The content of component G is preferably 0.01 to 1 part by weight, more preferably 0.05 to 0.8 parts by weight, and even more preferably 0.1 to 0.5 parts by weight, per 100 parts by weight of component A. If the content of component G is less than 0.01 parts by weight, sufficient impact resistance and flame retardancy cannot be obtained, and the appearance during molding may also deteriorate. If it exceeds 1 part by weight, thermal decomposition during molding may be promoted, resulting in insufficient impact resistance and a deterioration in the appearance during molding.

[0141] <Other ingredients> (i) Release agent The recycled polycarbonate resin composition of the present invention may contain a release agent to the extent that it exhibits the effects of the present invention, such as improving mold release properties during molding and reducing distortion of molded products.

[0142] Known release agents can be used. For example, 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 modification can also be used), silicone compounds (silicone oils, organosiloxanes, etc.), fluorine compounds (fluorine oils represented by polyfluoroalkyl ethers, etc.), paraffin wax, beeswax, etc. Among these, fatty acid esters are preferred as release agents.

[0143] Such fatty acid esters are esters of an aliphatic alcohol and an aliphatic carboxylic acid. Such aliphatic alcohol may be a monohydric alcohol or a polyhydric alcohol with two or more carbon atoms, preferably in the range of 3 to 32, and more preferably in the range of 5 to 30. Examples of such monohydric alcohols include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, ceryl alcohol, and triacontanol. Examples of such polyhydric alcohols include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol. In the fatty acid esters of the present invention, polyhydric alcohols are more preferred.

[0144] On the other hand, aliphatic carboxylic acids preferably have 3 to 32 carbon atoms, and aliphatic carboxylic acids with 10 to 22 carbon atoms are particularly preferred. Examples of such aliphatic carboxylic acids include saturated aliphatic carboxylic acids such as decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, behenic acid, eicosanic acid, and docosanic 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 with 14 to 20 carbon atoms are preferred. Saturated aliphatic carboxylic acids are more preferred among these. Stearic acid and palmitic acid are particularly preferred.

[0145] The above-mentioned aliphatic carboxylic acids, such as stearic acid and palmitic acid, are usually produced from natural oils and fats, such as animal fats and fats, represented by beef tallow and lard, and vegetable oils, represented by palm oil and sunflower oil. Therefore, these aliphatic carboxylic acids are usually mixtures containing other carboxylic acid components with different numbers of carbon atoms. Accordingly, in the production of fatty acid esters of the present invention, aliphatic carboxylic acids produced from such natural oils and fats, and in the form of mixtures containing other carboxylic acid components, particularly stearic acid and palmitic acid, are preferably used.

[0146] The above fatty acid ester may be either a partial ester or a full ester. However, since partial esters usually have a high hydroxyl value and tend to induce decomposition of resins at high temperatures, full esters are more preferable. 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. Note that 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. Note that the iodine value can be substantially 0. These properties can be determined by the method specified in JIS K 0070. The above-mentioned release agent may be a mixture of two or more types, not just one.

[0147] (ii) UV absorbers The recycled 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.

[0148] Benzotriazole-based UV 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-benzotriazole-2-yl)phenol], 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, and 2-(2-hydroxy-3,5-di-tert-butylphenyl) Examples include phenyl)-5-chlorobenzotriazole, 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-benzoxazine-4-one), and 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole. Examples of polymers having a 2-hydroxyphenyl-2H-benzotriazole skeleton include copolymers of 2-(2'-hydroxy-5-methacryloxyethylphenyl)-2H-benzotriazole with a vinyl monomer copolymerizable with the monomer, and copolymers of 2-(2'-hydroxy-5-acryloxyethylphenyl)-2H-benzotriazole with a vinyl monomer copolymerizable with the monomer.

[0149] Suitable examples of triazine-based UV absorbers include hydroxyphenyltriazine compounds such as 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-hexyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-methyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-ethyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-propyloxyphenol, and 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-butyloxyphenol. Furthermore, compounds in which the phenyl group of the above-exemplified hydroxyphenyltriazine compounds has been replaced with a 2,4-dimethylphenyl group, such as 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl)-5-hexyloxyphenol, are also exemplified. The above ultraviolet absorbers may be used individually or as a mixture of two or more.

[0150] (iii) dyes and pigments The recycled polycarbonate resin composition of the present invention contains various dyes and pigments, and can provide molded articles that exhibit diverse design properties. By incorporating fluorescent whitening agents or other fluorescent dyes that emit light, even better design effects can be imparted by utilizing the luminescent color. Furthermore, a recycled polycarbonate resin composition that is colored with a minute amount of dye and pigment and exhibits vivid color development can also be provided.

[0151] Examples of fluorescent dyes (including fluorescent whitening agents) used in the present invention include coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, perylene-based fluorescent dyes, anthraquinone-based fluorescent dyes, thioindigo-based fluorescent dyes, xanthene-based fluorescent dyes, xanthone-based fluorescent dyes, thioxanthene-based fluorescent dyes, thioxanthone-based fluorescent dyes, thiaidine-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 do not degrade much during the molding process of polycarbonate resin.

[0152] Other dyes besides the fluorescent dyes mentioned above 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 recycled polycarbonate resin composition of the present invention can also be blended with metallic pigments to obtain good metallic colors. Suitable metallic pigments include those having a metal coating or metal oxide coating on various plate-shaped fillers.

[0153] (iv) Other resins or elastomers The recycled polycarbonate resin composition of the present invention may also contain other resins or elastomers in small proportions, as long as they do not exert the effects of the present invention. Other resins include, for example, polyester resins such as polyethylene terephthalate resin and polybutylene terephthalate resin, polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polymethacrylate resins, phenolic resins, and epoxy resins. Examples of such elastomers include silicone rubber / isobutylene / isoprene rubber, ethylene / propylene rubber, acrylic elastomers, polyester elastomers, and polyamide elastomers.

[0154] (v) Other additives In addition, the recycled polycarbonate resin composition of the present invention may contain small amounts of well-known additives to impart various functions or improve the properties of molded articles. These additives are used in normal amounts, as long as they do not impair the objectives of the present invention. Examples of such additives include lubricants (e.g., PTFE particles), colorants (e.g., pigments and dyes other than the above-mentioned dyes, such as carbon black), light diffusing agents (e.g., acrylic crosslinked particles, silicone crosslinked particles, ultrathin glass flakes, etc.), inorganic phosphors (e.g., phosphors with aluminate as the matrix crystal), nucleating agents, radical generators, infrared absorbers (heat absorbers), and photochromic agents.

[0155] <Manufacturing of recycled polycarbonate resin composition> Any method can be used to produce the recycled polycarbonate resin composition according to the present invention. For example, components A to D and optionally other additives may be thoroughly mixed using premixing means such as a V-type blender, Henschel mixer, mechanochemical device, and extruder mixer, respectively. Then, if necessary, the premix may be granulated using an extruder granulator and briquetting machine, and after melt-kneading in a melt-kneader such as a vented twin-screw extruder, it may be pelletized using equipment such as a pelletizer.

[0156] <Manufacturing of molded articles made by injection molding of recycled polycarbonate resin composition> The recycled polycarbonate resin composition of the present invention can be used to manufacture various molded products by injection molding pellets obtained by the method described above. In such injection molding, it is possible to manufacture not only using the conventional cold runner molding method, but also using a hot runner that enables runnerless molding. Furthermore, in injection molding, not only conventional molding methods, but also 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, in-mold remelting molding, and molding methods consisting of combinations thereof can be used.

[0157] Furthermore, molded products formed from recycled polycarbonate resin compositions can undergo various surface treatments. These surface treatments include decorative coatings, hard coatings, water-repellent / oil-repellent coatings, hydrophilic coatings, UV-absorbing coatings, infrared-absorbing coatings, electromagnetic wave-absorbing coatings, heat-generating coatings, antistatic coatings, antistatic coatings, conductive coatings, and metallizing (plating, chemical vapor deposition (CVD), physical vapor deposition (PVD), thermal spraying, etc.).

[0158] <Flame-retardant> The combustion rating of a test specimen made from the recycled polycarbonate resin composition of the present invention in a vertical combustion test compliant with UL94 is preferably 5VB at a thickness of 1.5 mm and V-1 or higher at a thickness of 1.2 mm, and more preferably V-0 at a thickness of 1.5 mm. If such a combustion rating falls below 5VB at a thickness of 1.5 mm or V-1 at a thickness of 1.2 mm, it is difficult to apply the specimen to applications requiring a high degree of flame retardancy.

[0159] <Impact Resistance> The notched Charpy impact strength of the test specimen conforming to ISO 179 was 12 kJ / m². 2 The above is preferable, and 18 kJ / m³ 2 The above is more preferable: 30 kJ / m 2 The above is even more preferable. Below this preferable range, it is difficult to apply to various applications, and in particular, it is difficult to apply to housings and other applications where strength is required. The upper limit of the measured value of the notched Charpy impact strength is not particularly limited other than the limitations of the detection limit of the measuring instrument, but is 70 kJ / m 2 It performs optimally in the following situations. [Examples]

[0160] The present invention will be described in more detail below with reference to examples, but these examples are not intended to limit the present invention. Unless otherwise specified, parts in the examples are parts by weight, and % are weight percent. The evaluation was carried out according to the following method.

[0161] (Evaluation of recycled polycarbonate resin compositions) (1) Flame retardant In accordance with the UL 94 vertical combustion test specified by UL LLC (Underwriters Laboratories Limited Liability Company) in the United States, molded articles with thicknesses of 1.2 mm and 1.5 mm (width 12.5 mm, length 125 mm, thickness 1.2 mm or 1.5 mm) prepared using the method described below were used as test specimens for combustion testing. Flame retardancy was determined based on the results of these tests and evaluated by classifying them into 5VB, V-0, V-1, V-2, and notV.

[0162] (2) Impact resistance (Charpy impact strength with notch) The notched Charpy impact strength of test specimens (width 10 mm, length 80 mm, thickness 4.0 mm) prepared using the method described below was measured in accordance with ISO 179.

[0163] (3) Appearance during molding process The appearance of five ISO tensile and five ISO bending test specimens, obtained by molding after being left in a cylinder for 10 minutes under the same conditions as described below (cylinder temperature 280°C), was observed to check for the presence or absence of silver formation. ○: No silver was found on any of the test specimens. ×: Silver is present on one of the test pieces.

[0164] [Examples 1-16, Comparative Examples 1-8] The mixture was obtained by uniformly mixing components A to D and other components using a V-type blender, according to the compositions shown in Tables 1 to 3. Using a 30 mm screw diameter vented twin-screw extruder (manufactured by Japan Steel Works Ltd.; TEX30α-38.5BW-3V), the mixture was supplied from the supply port in a predetermined ratio using a meter. 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. After cooling the strands discharged from the die in a water bath, the strands were cut in a pelletizer to obtain pellets. A portion of the obtained pellets was dried in a hot air circulation dryer at 80-120°C for 5 hours, and then molded products for various evaluations were produced using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd.; SE130EV-A) at a cylinder temperature of 240-280°C and a mold temperature of 60°C.

[0165] The results of each evaluation are shown in Tables 1 to 3. The components represented by the symbols in Tables 1 to 3 are as follows: (Component A) A-1: Crushed material (viscosity-average molecular weight retention rate 90%) of Multilon TN-7500MC (manufactured by Teijin Limited, PC / ABS / phosphate ester / filler grade) recovered from the market. (B component) B-1: Aromatic polycarbonate resin [Manufactured by Teijin Limited; Panlite L-1250WP (product name), a linear aromatic polycarbonate resin powder with a viscosity-average molecular weight of 23,900, based on a repeating 2,2-bis(4-hydroxyphenyl)propane backbone] B-2 (Comparative Example): Aromatic polycarbonate resin [Manufactured by Teijin Limited; Panlite CM1000 (product name), a linear aromatic polycarbonate resin powder with a viscosity-average molecular weight of 15,000, with a repeating 2,2-bis(4-hydroxyphenyl)propane backbone] (C component) C-1: Butadiene-based impact modifier [(Manufactured by Kaneka Corporation; Kaneace M-724 (product name), a graft copolymer with a core-shell structure in which the core is mainly composed of butadiene rubber and the shell is mainly composed of methyl methacrylate and styrene, with an alkali metal content of 64 ppm] C-2: Butadiene-based impact modifier [Manufactured by Nippon A&L Co., Ltd.: SXH-330 (product name), an acrylonitrile-butadiene-styrene copolymer with an alkali metal content of 47 ppm, manufactured by emulsion polymerization] C-3 (Comparative Example) [(Manufactured by Kaneka Corporation; Kaneace M-701 (product name), a graft copolymer with a core-shell structure in which the core is mainly composed of butadiene rubber and the shell is mainly composed of methyl methacrylate and styrene, with an alkali metal content of 430 ppm)] (D component) D-1: Talc [(Manufactured by Katsumitsuyama Mining Co., Ltd.; Victorilite TK-RC (product name)] (E component) E-1: Phosphorus-based flame retardant [Manufactured by Daihachi Chemical Industry Co., Ltd.; CR-741 (product name), phosphate ester mainly composed of bisphenol A bis(diphenyl phosphate)] (F component) F-1: Polytetrafluoroethylene [Manufactured by Daikin Industries, Ltd.; Polyflon MPA FA-500H (product name), polytetrafluoroethylene] F-2: Polytetrafluoroethylene mixture [Manufactured by Shine Polymer; SN3307PF (product name), a polytetrafluoroethylene mixture consisting of polytetrafluoroethylene particles and a styrene-based organic polymer obtained by suspension polymerization (polytetrafluoroethylene content 50% by weight)] (G component) G-1: Phosphorus-based stabilizer [(Manufactured by ADEKA Corporation; ADEKA Stab 2112 (product name), Tris(2,4-di-tert-butylphenyl) phosphite)] G-2: Phenolic stabilizer [(Manufactured by ADEKA Corporation; ADEKA Stab AO-50 (product name), octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)] (Other ingredients) WAX: Fatty acid ester-based release agent [Manufactured by NOF Corporation; Unistar H-476-S (product name), pentaerythritol tetrastearate]

[0166] [Table 1]

[0167] [Table 2]

[0168] [Table 3]

[0169] From Tables 1 to 3, it can be seen that by adding polycarbonate resin, a butadiene-based impact modifier with an alkali metal content of 300 ppm or less, and silicate minerals in specific proportions to crushed polycarbonate resin molded products, a recycled polycarbonate resin composition can be obtained that has properties equivalent to the impact resistance, flame retardancy, and appearance characteristics during molding that the original resin composition possessed.

Claims

1. A recycled polycarbonate resin composition characterized by containing, per 100 parts by weight of (A) crushed polycarbonate resin molded product (component A), (B) 1 to 60 parts by weight of polycarbonate resin with a viscosity-average molecular weight of 17,000 or more (component B), (C) 0.5 to 35 parts by weight of a butadiene-based impact modifier with an alkali metal content of 300 ppm or less (component C), (D) 0.01 to 20 parts by weight of silicate mineral (component D), and (E) 30 parts by weight or less of a phosphorus-based flame retardant (component E).

2. The recycled polycarbonate resin composition according to claim 1, characterized in that the viscosity-average molecular weight of the polycarbonate resin in component A is 80% or more of the viscosity-average molecular weight of the polycarbonate resin in component A, which is a virgin raw material.

3. The recycled polycarbonate resin composition according to claim 1 or 2, characterized in that it contains 0.01 to 2 parts by weight of (F) a drip inhibitor (component F) per 100 parts by weight of component A.

4. The recycled polycarbonate resin composition according to claim 1 or 2, characterized in that it contains 0.01 to 1 part by weight of at least one stabilizer (component G) selected from the group consisting of phosphorus-based stabilizers and phenol-based stabilizers, per 100 parts by weight of component A.

5. A molded article obtained by injection molding the recycled polycarbonate resin composition according to claim 1 or 2.

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